CN105419348A - Resin composition and presoaking material and laminated board using same - Google Patents
Resin composition and presoaking material and laminated board using same Download PDFInfo
- Publication number
- CN105419348A CN105419348A CN201510852434.9A CN201510852434A CN105419348A CN 105419348 A CN105419348 A CN 105419348A CN 201510852434 A CN201510852434 A CN 201510852434A CN 105419348 A CN105419348 A CN 105419348A
- Authority
- CN
- China
- Prior art keywords
- epoxy resin
- resin
- polyphenylene oxide
- epoxy
- kinds
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000011342 resin composition Substances 0.000 title claims abstract description 12
- 239000000463 material Substances 0.000 title abstract description 9
- 229920005989 resin Polymers 0.000 claims abstract description 230
- 239000011347 resin Substances 0.000 claims abstract description 230
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 173
- 229920006380 polyphenylene oxide Polymers 0.000 claims abstract description 173
- CMLFRMDBDNHMRA-UHFFFAOYSA-N 2h-1,2-benzoxazine Chemical compound C1=CC=C2C=CNOC2=C1 CMLFRMDBDNHMRA-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000003822 epoxy resin Substances 0.000 claims description 211
- 229920000647 polyepoxide Polymers 0.000 claims description 211
- 230000004048 modification Effects 0.000 claims description 96
- 238000012986 modification Methods 0.000 claims description 96
- 229920000642 polymer Polymers 0.000 claims description 73
- 239000000203 mixture Substances 0.000 claims description 58
- 238000006243 chemical reaction Methods 0.000 claims description 40
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 37
- 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
- 238000003756 stirring Methods 0.000 claims description 31
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 26
- 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
- 238000005470 impregnation Methods 0.000 claims description 19
- 229940106691 bisphenol a Drugs 0.000 claims description 17
- 150000001412 amines Chemical class 0.000 claims description 16
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 claims description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- -1 cyclic crown ether Chemical class 0.000 claims description 15
- 239000004593 Epoxy Substances 0.000 claims description 13
- 239000003795 chemical substances by application Substances 0.000 claims description 13
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 13
- 239000007787 solid Substances 0.000 claims description 13
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 12
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 12
- 239000003054 catalyst Substances 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
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical class C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- 125000000524 functional group Chemical group 0.000 claims description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 8
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 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 compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 239000002585 base Substances 0.000 claims description 6
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 claims description 6
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 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
- 239000003513 alkali Substances 0.000 claims description 5
- 239000004843 novolac epoxy resin Substances 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 5
- 229920002379 silicone rubber Polymers 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
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-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
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical compound CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 claims description 4
- 125000001118 alkylidene group Chemical group 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
- SQNZJJAZBFDUTD-UHFFFAOYSA-N durene Chemical compound CC1=CC(C)=C(C)C=C1C SQNZJJAZBFDUTD-UHFFFAOYSA-N 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 class 0.000 claims description 4
- 239000012764 mineral filler Substances 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
- 150000003222 pyridines Chemical class 0.000 claims description 4
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 4
- 150000003512 tertiary amines Chemical class 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
- 229920001187 thermosetting polymer Polymers 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
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 239000006185 dispersion Substances 0.000 claims description 3
- 229940015043 glyoxal Drugs 0.000 claims description 3
- WHJMGMTWMIGGQF-UHFFFAOYSA-N 1,1'-biphenyl;methanamine Chemical compound NC.C1=CC=CC=C1C1=CC=CC=C1 WHJMGMTWMIGGQF-UHFFFAOYSA-N 0.000 claims description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 2
- RMHQDKYZXJVCME-UHFFFAOYSA-N 2-pyridin-4-ylpyridine Chemical group N1=CC=CC=C1C1=CC=NC=C1 RMHQDKYZXJVCME-UHFFFAOYSA-N 0.000 claims description 2
- MWVTWFVJZLCBMC-UHFFFAOYSA-N 4,4'-bipyridine Chemical compound C1=NC=CC(C=2C=CN=CC=2)=C1 MWVTWFVJZLCBMC-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
- 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
- YJLYANLCNIKXMG-UHFFFAOYSA-N N-Methyldioctylamine Chemical compound CCCCCCCCN(C)CCCCCCCC YJLYANLCNIKXMG-UHFFFAOYSA-N 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
- WHKUVVPPKQRRBV-UHFFFAOYSA-N Trasan Chemical compound CC1=CC(Cl)=CC=C1OCC(O)=O WHKUVVPPKQRRBV-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 150000005130 benzoxazines Chemical class 0.000 claims description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Substances FB(F)F WTEOIRVLGSZEPR-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
- 238000005660 chlorination reaction Methods 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
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 2
- 150000001983 dialkylethers Chemical class 0.000 claims description 2
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 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
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 150000007517 lewis acids Chemical class 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
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 239000012188 paraffin wax Substances 0.000 claims description 2
- 229920001568 phenolic resin Polymers 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
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 2
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 claims description 2
- CEYYIKYYFSTQRU-UHFFFAOYSA-M trimethyl(tetradecyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCC[N+](C)(C)C CEYYIKYYFSTQRU-UHFFFAOYSA-M 0.000 claims description 2
- 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 description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 239000004744 fabric Substances 0.000 abstract description 19
- 239000003365 glass fiber Substances 0.000 abstract description 3
- 238000002360 preparation method Methods 0.000 description 51
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 32
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 31
- 238000003825 pressing Methods 0.000 description 30
- 239000002904 solvent Substances 0.000 description 28
- 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
- 150000002118 epoxides Chemical group 0.000 description 18
- 239000011521 glass Substances 0.000 description 16
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 description 16
- 235000012239 silicon dioxide Nutrition 0.000 description 16
- 239000000377 silicon dioxide Substances 0.000 description 15
- 229960001866 silicon dioxide Drugs 0.000 description 15
- 238000007731 hot pressing Methods 0.000 description 14
- 238000000034 method Methods 0.000 description 14
- 229920003986 novolac Polymers 0.000 description 14
- 238000011056 performance test Methods 0.000 description 14
- 239000000758 substrate Substances 0.000 description 14
- 230000035484 reaction time Effects 0.000 description 9
- 239000008096 xylene Substances 0.000 description 8
- 239000002245 particle Substances 0.000 description 7
- 239000000843 powder Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 4
- 229920001955 polyphenylene ether Polymers 0.000 description 4
- 0 CC(c1c(*)c(I)c(C(C)(C)*C(C)(C[C@](C=*)c2c(*)c(*C(*)*C3OC3)c3[Tl+])*2c3[Tl])c(*)c1C)O*C(*)*C1OC1 Chemical compound CC(c1c(*)c(I)c(C(C)(C)*C(C)(C[C@](C=*)c2c(*)c(*C(*)*C3OC3)c3[Tl+])*2c3[Tl])c(*)c1C)O*C(*)*C1OC1 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
- 230000008901 benefit Effects 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000000835 fiber 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
- 238000009413 insulation Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- 238000007711 solidification Methods 0.000 description 3
- 230000008023 solidification Effects 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
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-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
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 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
- 229910003460 diamond Inorganic materials 0.000 description 2
- 239000010432 diamond Substances 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 238000005516 engineering process Methods 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
- 239000003112 inhibitor Substances 0.000 description 2
- 239000011256 inorganic filler Substances 0.000 description 2
- 229910003475 inorganic filler Inorganic materials 0.000 description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 2
- 239000000347 magnesium hydroxide Substances 0.000 description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 229920013636 polyphenyl ether polymer Polymers 0.000 description 2
- 229910010271 silicon carbide Inorganic materials 0.000 description 2
- 229910000679 solder Inorganic materials 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 235000012222 talc Nutrition 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 description 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
- 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
- 229920001730 Moisture cure polyurethane Polymers 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
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 230000000996 additive effect Effects 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
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 229910052799 carbon Inorganic materials 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
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000004132 cross linking 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
- 229920001971 elastomer Polymers 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 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
- 239000003292 glue Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 238000010438 heat treatment 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
- 238000010030 laminating Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 235000014380 magnesium carbonate Nutrition 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 229960001708 magnesium carbonate Drugs 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 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
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-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
- 238000002203 pretreatment Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 230000008054 signal transmission Effects 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 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
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000003068 static effect Effects 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
- 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
- 238000009736 wetting Methods 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- XAEWLETZEZXLHR-UHFFFAOYSA-N zinc;dioxido(dioxo)molybdenum Chemical compound [Zn+2].[O-][Mo]([O-])(=O)=O XAEWLETZEZXLHR-UHFFFAOYSA-N 0.000 description 1
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
-
- 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
- B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
-
- 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
- B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
- B32B37/15—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer being manufactured and immediately laminated before reaching its stable state, e.g. in which a layer is extruded and laminated while in semi-molten state
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
-
- 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
-
- 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
- B32B2250/00—Layers arrangement
- B32B2250/40—Symmetrical or sandwich layers, e.g. ABA, ABCBA, ABCCBA
-
- 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
- B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
- B32B2260/02—Composition of the impregnated, bonded or embedded layer
- B32B2260/021—Fibrous or filamentary layer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
- B32B2260/04—Impregnation, embedding, or binder material
- B32B2260/046—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
- B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
- B32B2262/10—Inorganic fibres
- B32B2262/101—Glass fibres
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2270/00—Resin or rubber layer containing a blend of at least two different polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/306—Resistant to heat
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/306—Resistant to heat
- B32B2307/3065—Flame resistant or retardant, fire resistant or retardant
-
- 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
- B32B2457/00—Electrical equipment
- B32B2457/08—PCBs, i.e. printed circuit boards
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Abstract
The invention provides a resin composition and a presoaking material and laminated board using the same. The resin composition comprises a prepolymer of epoxy-resin-modified polyphenylene oxide resin and benzoxazine resin. According to the resin composition and the presoaking material and laminated board using the same, the prepolymer of the epoxy-resin-modified polyphenylene oxide resin is used for the resin composition of a printed circuit board, the dielectric property of a copper-clad plate can be improved, the wettability of glass fibre cloth made of the resin composition containing the prepolymer of the epoxy-resin-modified polyphenylene oxide resin can be improved, and the obtained resin composition can have excellent appearance, heat resistance, dielectric property and peeling strength.
Description
Technical field
The invention belongs to copper-clad plate technical field, be specifically related to a kind of resin combination and use its prepreg and veneer sheet.
Background technology
Polyphenylene oxide resin has excellent water tolerance, dimensional stability, flame retardant properties and dielectric properties, and obtains the more excellent resin combination of over-all properties by mixing with other.Thus be widely used in various field as starting material, and such as, plumbing fixtures (plumbingfixtures), electrical appliance kit, trolley part, and coated wire, copper-clad laminate and printed wiring etc.
Though outstanding dielectric properties can be obtained based on the copper-clad laminate of polyphenylene oxide resin, but in prior art application, only employing polyphenylene oxide resin and other resin combination carry out the glue varnish that simple physical blending becomes homogeneous, impregnated in glasscloth surface and obtain semicure film, and then be cured the series of processes such as pressing and obtain copper foil laminated.Because polyphenylene oxide resin polarity is lower, poor with the consistency of other resin in resin combination, carry out affecting the apparent of prepreg; In addition, the impregnation of polyphenylene oxide resin and glasscloth is also undesirable, is easily gathered into film in glass cloth surface, and this also can affect the apparent of prepreg, and then has a negative impact to the dielectric properties of product.
Publication number is a kind of method that the patent of CN1556830 proposes functionalized polyphenylene ether, react under the effect of amines catalyst by polyphenylene oxide and bisphenol A type epoxy resin, obtain the polyphenylene oxide/epoxy resin prepolymer that two end groups have two epoxide groups respectively, the method improves the application problem of polyphenylene oxide mentioned above to a certain extent, but the bisphenol A type epoxy resin introduced but creates disadvantageous effect-its Dk/Df is increased to the dielectric properties of molecular resin.
Summary of the invention
An object of the present invention is to provide a kind of resin combination, it adopts epoxy resin modification polyphenylene oxide resin performed polymer to coordinate with benzoxazine colophony, makes it have excellent appearance, the thermotolerance (Tg that DSC method records reaches 180-210 DEG C) of superelevation and the dielectric properties of excellence and stripping strength.
To achieve these goals, present invention employs following technical scheme:
A kind of resin combination, this resin combination comprises performed polymer and the benzoxazine colophony of epoxy resin modification polyphenylene oxide resin.
The present invention, by polyphenylene oxide resin being modified as the polyphenylene oxide epoxy prepolymer with group, then with benzoxazine colophony complex reaction, combines the low dielectric of polyphenylene oxide resin and heat-resisting, the high Tg of height of benzoxazine colophony and fire-retardant advantage simultaneously.Therefore, resin combination containing epoxide modified polyphenylene oxide resin performed polymer and benzoxazine is used in the resin combination of printed circuit board (PCB), the dielectric properties of copper-clad plate can not only be improved, and improve the glass fiber cloth infiltrating of the resin combination of the performed polymer containing this epoxy resin modification polyphenylene oxide resin, make the resin combination obtained have excellent appearance, thermotolerance, dielectric properties and stripping strength and high Tg.
Preferably, the performed polymer of described epoxy resin modification polyphenylene oxide resin has the structure as shown in formula I:
Wherein, X is:
Wherein, R is alkylidene group, the singly-bound ,-SO of substituted or unsubstituted C1 ~ C5
2-,-O-,-CO-,-SO-or-SC-;
Y is the functional group of functional epoxy resin;
Z
1, Z
2, Z
3, Z
4identical or different, be hydrogen atom, halogen atom, the alkyl (such as C1, C2, C3, C4, C5, C6 or C7) of carbonatoms less than 8 or phenyl all independently;
N be greater than 1 positive integer.It should be noted that, n represents the polymerization degree of macromolecular compound, above-mentioned various and enumerate below various in, n gets identical or different value respectively.
Preferably, in formula I, X is
Preferably, described polyphenylene oxide resin molecular structure is as shown in formula II:
Wherein, X is:
Wherein, R is alkylidene group, the singly-bound ,-SO of substituted or unsubstituted C1 ~ C5
2-,-O-,-CO-,-SO-or-SC-;
Z
1, Z
2, Z
3, Z
4identical or different, be hydrogen atom, halogen atom, the alkyl (such as C1, C2, C3, C4, C5, C6 or C7) of carbonatoms less than 8 or phenyl all independently;
N be greater than 1 positive integer.
Preferably, the X in formula II is:
Preferably, the molecular structural formula of described polyphenylene oxide resin is such as formula shown in (III) or formula (IV):
N be greater than 1 positive integer.
Preferably, described functional 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, Study On O-cresol Epoxy Resin, trifunctional base epoxy, four functional group's epoxy resin, Dicyclopentadiene (DCPD) epoxy resin, p-aminophenol epoxy resin, tricyanic epoxy resin, phosphorous epoxy resin, nitrogen-containing epoxy thermoset, p-Xylol epoxy resin, naphthalene type epoxy resin, benzo croak is muttered type epoxy resin, the mixture of any one or at least two kinds in xenol formaldehyde epoxy resin or phenolic group benzene alkyl phenolic epoxy resin.
Preferably, in formula (I), Y is any one in following structure:
Wherein, the positive integer of m and n all independently for being greater than 1.
Preferably, the performed polymer of described epoxy resin modification polyphenylene oxide resin is reacted as follows by solid-state polyphenylene oxide resin and epoxy resin and obtained:
By epoxy resin 20-80 weight part and catalyzer 0.005 ~ 10 weight part, dissolve in intensification and under stirring; Again by solid-state polyphenylene oxide resin 50 weight part, be dissolved in organic solvent and make the polyphenylene oxide resin solution that solid content is 30 ~ 70%, then it is slowly added dropwise in above-mentioned epoxy resin molten mass, after dropwising under 125 ~ 160 DEG C (such as 125 DEG C, 130 DEG C, 135 DEG C, 140 DEG C, 145 DEG C, 150 DEG C or 155 DEG C) stirring reaction 3.5-12 hour (such as 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, 10 hours or 11 hours), the prepolymer solution of obtained epoxy resin modification polyphenylene oxide resin.
In the performed polymer preparation process of epoxy resin modification polyphenylene oxide resin, there is important impact for the quality of product and preparation efficiency in temperature of reaction and reaction times.When temperature of reaction is lower than 125 DEG C, no matter the reaction times how long, the hydroxyl of epoxide group and polyphenylene oxide reacts hardly, and temperature of reaction then can cause epoxy autohemagglutination to be even cross-linked side reaction such as grade higher than 160 DEG C greatly to be increased, all cannot obtain epoxide modified polyphenylene oxide performed polymer; When temperature of reaction is higher than 125 DEG C, if the reaction times is less than 3.5 hours, polyphenylene oxide terminal functional group fully can not connect epoxide functional groups, thus affect the improvement effect of epoxide modified polyphenylene oxide resin in resin combination, if the reaction times is longer than 12 hours, side reaction can be caused to produce and cause epoxide group autohemagglutination.
The advantage of the preparation method of the performed polymer of epoxy resin modification polyphenylene oxide resin of the present invention is adopted to be:
Utilize high boiling solvent as reaction solvent, the temperature of reaction that not only can improve pre-polymerization makes reaction carry out smoothly, and the low volatility of solvent can also provide stable reaction environment.In addition, catalyzer used in the present invention can the reaction of optionally preferential catalysis epoxy and polyphenylene oxide terminal hydroxy group, obtain epoxide modified polyphenylene oxide performed polymer target product, avoid the self-polymeric reaction of epoxy resin itself and the overreact caused, cause that the molecular weight of product is excessive, cross-linking set is few, reduce the intensity of resin solidification body.As prepared the performed polymer of the epoxy resin modification polyphenylene oxide resin of same structure, the preparation method adopted is: by the liquid polyphenylene oxide resin solution of melt into after solid-state polyphenylene oxide resin 100 parts, interpolation polymerization solvent, again by epoxy resin 24-35 part and imidazoles catalyzer 0.001-5 part, add in solution, under 100-120, be uniformly mixed 1-3 hour and obtained pre-polymer solution.The organic solvent boiling point that the method adopts is low, easily volatilizees under radical reaction problem, or causes its temperature of reaction unstable.In addition, the method have ignored the self-polymeric reaction of epoxy resin itself, thus causes overreact, causes the molecular weight of product excessive, reduces the intensity of resin solidification body.
Preferably, described catalyzer is the mixture of any one or at least two kinds in polyethers, cyclic crown ether class, amine, inorganic strong alkali or inorganic acid.
Preferably, described polyethers is chain polyoxyethylene glycol (H-(OCH2CH2)
n-OH) or/and chain dialkylethers (R (OCH2CH2)
n-OR) etc.
Preferably, described cyclic crown ether class is the mixture that 18 hats 6,15 are preced with any one or at least two kinds in 5 or cyclodextrin etc.
Preferably, described amine is the mixture of any one or at least two kinds in quaternary ammonium salt, tertiary amine or pyridine compounds.
Preferably, described quaternary ammonium salt is the mixture of any one or at least two kinds in benzyltriethylammoinium chloride (TEBA), Tetrabutyl amonium bromide, tetrabutylammonium chloride, 4-butyl ammonium hydrogen sulfate (TBAB), tri-n-octyl methyl ammonium chloride, Dodecyl trimethyl ammonium chloride or tetradecyl trimethyl ammonium chloride etc.;
Preferably, described tertiary amine is R
3n, wherein R be the branched-chain or straight-chain alkyl of carbonatoms less than 18, replacement or the phenyl that do not replace, the mixture of any one or at least two kinds in preferred triethylamine, Tributylamine, dioctylmethylamine or phenylbenzene methylamine etc.
Preferably, described pyridine compounds be pyridine, mixture with any one in less than 8 carbon atom side chains or the substituent pyridine of straight-chain paraffin, phenylpyridine or dipyridyl etc. or at least two kinds.
Preferably, described dipyridyl is 2,2 '-dipyridyl, 4,4'-Bipyridine, 2,4 '-dipyridyl or 2, the mixture of any one or at least two kinds in 3 '-dipyridyl.
Preferably, described inorganic strong alkali is that sodium hydroxide is or/and potassium hydroxide.
Preferably, described inorganic acid is the mixture of any one or at least two kinds in the vitriol oil, hydrochloric acid or nitric acid etc.
Preferably, the temperature of described stirring reaction is 135-150 DEG C, and the time of stirring reaction is 4-8 hour.
Preferably, described organic solvent is the mixed solvent of any one or at least two kinds in DMF, N, N-diethylformamide, pimelinketone, toluene, dimethylbenzene, trimethylbenzene or durene.
In the performed polymer preparation process of epoxy resin modification polyphenylene oxide resin, there is important impact for the quality of product and preparation efficiency in raw materials used proportioning and the consumption of catalyzer.
With parts by weight, relative to the polyphenylene oxide resin of 50 weight parts, if epoxy resin is less than 20 weight parts, then polyphenylene oxide terminal functional group fully can not connect epoxide functional groups, thus the epoxy group(ing) affecting polyphenylene oxide resin improves efficiency; If epoxy resin is more than 80 weight parts, then after having reacted, too much epoxy resin can affect the formulating of recipe of resin combination.Preferably, the addition of epoxy resin is 30 ~ 70 weight parts, is preferably 40 ~ 60 weight parts.In addition, if catalyzer is less than 0.005 weight part, speed of reaction is comparatively slow, causes the reaction times elongated, affects reaction efficiency and cost; If catalyzer is more than 10 weight parts, speed of reaction can be made too fast, cause side reaction produce and cause epoxide group autohemagglutination.Preferably, the addition of catalyzer is 0.005 ~ 5 weight part, preferably 0.005 ~ 1 weight part.
Preferably, described method is: by solid-state polyphenylene oxide resin 50 parts, the liquid polyphenylene oxide resin solution of melt into after interpolation polymerization solvent, then by epoxy resin 30-70 part and catalyzer 0.005 ~ 1 part, add in solution, stirring reaction 4 ~ 8 hours at 130 ~ 150 DEG C and prepolymer solution.
Preferably, in resin combination, the addition of the performed polymer of epoxy resin modification polyphenylene oxide resin is 20-80 weight part.
Preferably, in resin combination, the content of described benzoxazine colophony is 10-60 weight part, such as 15 weight parts, 20 weight parts, 25 weight parts, 30 weight parts, 35 weight parts, 40 weight parts, 45 weight parts, 50 weight parts or 55 weight parts.
Preferably, described benzoxazine colophony is the mixture of any one or at least two kinds in bisphenol A benzoxazine, Bisphenol F benzoxazine, bisphenol S benzoxazine, two amine type benzoxazines, phenolphthalein type benzoxazine or dicyclopentadiene-type benzoxazine.
Preferably, also comprise solidifying agent in described resin combination, its content is 5 ~ 50 weight parts.
Preferably, described solidifying agent is selected from any one or the two or more mixtures in linear phenolic resin, Zelan 338 resin, DDS or DDM etc.
Preferably, also comprise curing catalyst in described resin combination, its content is 0.01 ~ 10 weight part.
Resin combination disclosed by the present invention, there is important impact for the quality of product, preparation efficiency in raw materials used consumption.Specifically, relative to the performed polymer of the epoxy resin modification polyphenylene oxide resin of 50-90 weight part, if solidifying agent is less than 5 weight parts, then the epoxide functional groups of the performed polymer end of epoxy resin modification polyphenylene oxide resin fully can not react solidification, makes the Tg of composition (glass transition temp) too low; If solidifying agent is more than 50 weight parts, excessive unreacted linking agent can be remained, make the performances such as the thermotolerance of composition, Tg not good.
If curing catalyst is less than 0.01 weight part, answer speed comparatively slow, without obvious catalytic effect; If curing catalyst is more than 10 weight parts, makes speed of reaction too fast, affect the preparation process of product and the quality of product.
Preferably, described curing catalyst is selected from imidazoles (imidazole), boron trifluoride amine compound, chlorination Yi base triphenyl phosphonium (ethyltriphenylphosphoniumchloride), glyoxal ethyline (2-methylimidazole, 2-MI), 2-phenylimidazole (2-phenyl-1H-imidazole, 2PZ), 2-ethyl-4-methylimidazole (2-ethyl-4-methylimidazole, 2E4MZ), triphenylphosphine (tri-phenylphosphine, or 4-dimethylaminopyridine (4-dimethylaminopyridine TPP), the lewis base of the combination of any one or at least two kinds DMAP), or be selected from manganese, iron, cobalt, nickel, the lewis acid of the metal salt compound of any one or at least two kinds in copper or zinc, or be selected from organo-peroxide, as dicumyl peroxide (DCP, DicumylPeroxide).
Preferably, described resin composition comprise further 5 ~ 60 weight parts (such as 10 weight parts, 15 weight parts, 20 weight parts, 25 weight parts, 30 weight parts, 35 weight parts, 40 weight parts, 45 weight parts, 50 weight parts or 55 weight parts) without prepolymerized epoxy resin.
Preferably, described 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, Study On O-cresol Epoxy Resin, trifunctional base epoxy, four functional group's epoxy resin, Dicyclopentadiene (DCPD) epoxy resin, p-aminophenol epoxy resin, tricyanic epoxy resin, phosphorous epoxy resin, nitrogen-containing epoxy thermoset, brominated epoxy resin, p-Xylol epoxy resin, naphthalene type epoxy resin, benzo croak is muttered type epoxy resin, any one or two or more mixtures in xenol formaldehyde epoxy resin or phenolic group benzene alkyl phenolic epoxy resin.
Preferably, the mixture of any one or at least two kinds in mineral filler, fire retardant, interfacial agent, dispersion agent, silicone elastomer or toughner is comprised in described resin combination further.
Preferably, described mineral filler comprises silicon-dioxide (molten state or non-melt state and Porous), aluminum oxide, magnesium oxide, magnesium hydroxide, calcium carbonate, aluminium nitride, boron nitride, aluminium hydroxide, aluminum silicon carbide, silicon carbide, sodium carbonate, titanium dioxide, zinc oxide, zirconium white, quartz, diamond dust, class diamond dust, graphite, magnesiumcarbonate, potassium titanate, ceramic fiber, mica, boehmite (boehmite, ALOOH), high temperature resistant aluminium hydroxide (ALH), zinc molybdate, ammonium molybdate, zinc borate, calcium phosphate, calcination of talc, talcum, silicon nitride, section burns kaolin, clay, alkali magnesium sulfate crystal whisker, barium sulfate, magnesium hydroxide crystal whisker, magnesia crystal whisker, calcium oxide whisker, carbon nanotube, how meter level inorganic powder or tool organic core outer shell are the mixture of any one or at least two kinds in the powder particle of isolator modification, and mineral filler is ball-type or pin palpus shape, or selectivity is via surfactants pre-treatment.
In addition, in order to ensure the dielectric properties that finished product is good, inorganic filler is the particle powder of particle diameter less than 100 μm, is preferably the particle powder of particle diameter 1-20 μm, and optimum is particle diameter 1 μm with down to nano-sized particles sprills.Pin shape inorganic filler must be diameter less than 50 μm and length is the powder of 1-200 μm.
Preferably, described fire retardant is selected from the one or more kinds of combinations of phosphonium flame retardant, nitrogenous flame ratardant or brominated flame-retardant.Wherein, common phosphonium flame retardant is as OP-935, SPB-100 or PX-200; Nitrogenous flame ratardant is as MelamineCyanurate, and brominated flame-retardant, as TBBPA or Tetra-Bromo-bisphenolA, in its technical scheme all used in the present invention, and reaches good flame retardant effect.
Preferably, described interfacial agent (or claim siloxanes coupler, siloxane) known person can be used, be not particularly limited, specifically, vinyltriethoxysilane, vinyltrimethoxy silane, vinyl is preferably used to join ('beta '-methoxy-Ethoxysilane), γ-glycidoxypropyltrime,hoxysilane or γ-amine propyl-triethoxysilicane.What wherein dispersion agent was conventional has the products such as German Bi Ke BYK-103, BYK-901, BYK-161 and BYK-164, but not as limit.
Preferably, described silicone elastomer (hybridtypesiliconepowder) is rubber and resin type composite granule, is preferably spherical powder.Add thermotolerance and impact absorbency that silicone elastomer can increase this resin combination.The products such as X-52-7030, KMP-605, KMP-602, KMP-601, KMP-600, KMP-590 and KMP-594 that generally commercially available silicone elastomer is produced as SHIN-ETSU HANTOTAI, but not as limit.
" comprising " of the present invention, mean it except described component, can also comprise other components, these other components give described resin combination different characteristics.In addition, " comprising " of the present invention, can also replace with enclosed " being " or " by ... composition ".
Such as, described silicon resin composition can also contain various additive, as concrete example, can enumerate oxidation inhibitor, thermo-stabilizer, static inhibitor, UV light absorber, pigment, tinting material or lubricant etc.These various additives can be used alone, also can two kinds or two or more used in combination.
Two of object of the present invention is to provide a kind of prepreg, and it comprises strongthener and by the as above resin combination of the dry postadhesion of impregnation on strongthener.
Described strongthener adopts natural fiber, organic synthetic fibers, organic fabric or inorganic fibre to make.
Three of object of the present invention is to provide a kind of veneer sheet, and described veneer sheet contains at least one prepreg as above, and it is by obtaining shaping at least one prepreg heating and pressurizing as above.
Four of object of the present invention is to provide a kind of copper-clad laminate, and described copper-clad laminate comprises at least one superimposed prepreg as above and covers the Copper Foil of one or both sides of the prepreg after superimposed.
Five of object of the present invention is to provide a kind of printed wiring veneer sheet, and it contains at least one prepreg as above.Adopt the circuit card that above-mentioned veneer sheet is made, good thermotolerance and dielectric properties can be shown, be conducive to the Signal transmissions of HF link plate.
Compared with the prior art, the present invention has following beneficial effect:
The present invention, by polyphenylene oxide resin being modified as the polyphenylene oxide epoxy prepolymer with group, then with benzoxazine colophony complex reaction, combines the low dielectric of polyphenylene oxide resin and heat-resisting, the high Tg of height of benzoxazine colophony and fire-retardant advantage simultaneously.Therefore, resin combination containing epoxide modified polyphenylene oxide resin performed polymer and benzoxazine is used in the resin combination of printed circuit board (PCB), the dielectric properties of copper-clad plate can not only be improved, and improve the glass fiber cloth infiltrating of the resin combination of the performed polymer containing this epoxy resin modification polyphenylene oxide resin, make the resin combination obtained have excellent appearance, thermotolerance, dielectric properties and stripping strength and high Tg.
In addition, the method of disclosed synthetic epoxy resin modified polyphenylene ether resin performed polymer, synthetic technology as compared with the past, because selecting different catalysts, solvent, reaction times and temperature of reaction etc., effectively inhibit side reaction---the reaction of epoxy resin autohemagglutination, can effectively make the molecular weight of performed polymer product reach or close to theoretical value.
And, the aggressiveness that the epoxy resin modification polyphenylene oxide resin obtained adopting the preparation method of the pre-aggressiveness of disclosed epoxy resin modification polyphenylene oxide resin is pre-, coordinate with benzoxazine colophony, the laminating material obtained and copper clad laminate, it has good appearance, the thermotolerance (Tg that DSC method records reaches 180-210 DEG C) of superelevation and the dielectric properties of excellence and stripping strength.
In addition, the method for the performed polymer of disclosed epoxy resin modification polyphenylene oxide resin is easy and simple to handle, and production process environmental protection is with low cost, has the feasibility of scale operation.
To sum up, the Tg of the veneer sheet adopting resin combination of the present invention to obtain can reach 180 ~ 210 DEG C, stripping strength can reach 1.51 ~ 1.71N/cm, test by PCT (3hr), resistance to immersed solder (288 DEG C) is greater than 20min, under 1G, Dk can reach 3.75 ~ 3.87, Df is 0.005 ~ 0.008.
Accompanying drawing explanation
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.
Embodiment
Technical scheme of the present invention is further illustrated below by embodiment.
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 bisphenol A type epoxy resin 50 parts and pyridine 0.005 part, dissolve in intensification and under stirring; Again by solid-state polyphenylene oxide resin 50 parts, be dissolved in xylene solvent and make the polyphenylene oxide resin solution that solid content is 30 ~ 70%, slowly be added dropwise in above-mentioned epoxy resin molten mass, after dropwising at 145 DEG C stirring reaction 6 hours and the prepolymer solution of epoxy resin modification polyphenylene oxide resin.Epoxy resin, the GPC figure of the performed polymer product of polyphenylene oxide and epoxy resin modification polyphenylene oxide resin respectively as shown in Figure 1, Figure 2 and Figure 3.
(2) preparation of the performed polymer composition of epoxy resin modification polyphenylene oxide resin
The phosphonium flame retardant (PX-200, large eight chemistry of Japan) of the molten state silicon-dioxide of the 2-MI of the phenol novolacs of the performed polymer of step (1) the epoxy resin modification polyphenylene oxide resin of 60 weight parts, 20 weight parts, 40 parts by weight of bisphenol A type benzoxazine colophonies, 0.1 weight part, 100 weight parts, 20 weight parts and the butanone solvent of 30 weight parts are mixed, are uniformly dispersed.
(3) semicure of resin combination and the preparation of substrate
By the performed polymer composition of above-mentioned epoxy resin modification polyphenylene oxide resin through with the impregnation of glass cloth after, 170 DEG C baking 3 minutes make prepreg, prepreg outward appearance enters shown in table one; Again two panels Copper Foil is coincided in obtained 4 prepreg both sides, adopt vacuum hotpressing machine, at temperature 190 DEG C, pressure 35kg/cm
2, under pressing time 90min condition, pressing and forming, to obtain a kind of copper foil laminates, performance test as shown in Table 2.
Embodiment two
(1) the prepolymer solution preparation of epoxy resin modification polyphenylene oxide resin:
By DCPD epoxy resin 50 parts and pyridine 0.005 part, dissolve in intensification and under stirring; Again by solid-state polyphenylene oxide resin 50 parts, be dissolved in xylene solvent and make the polyphenylene oxide resin solution that solid content is 30 ~ 70%, slowly be added dropwise in above-mentioned epoxy resin molten mass, after dropwising at 145 DEG C stirring reaction 6 hours and the prepolymer solution of epoxy resin modification polyphenylene oxide resin.Utilize in the molecular weight determination of GPC at the performed polymer of the epoxy resin modification polyphenylene oxide resin of gained, weight-average molecular weight is 6200.
(2) preparation of the performed polymer composition of epoxy resin modification polyphenylene oxide resin
The phosphonium flame retardant (PX-200, large eight chemistry of Japan) of the molten state silicon-dioxide of the 2-MI of the phenol novolacs of the performed polymer of step (1) the epoxy resin modification polyphenylene oxide resin of 60 weight parts, 20 weight parts, 40 weight part two amine type benzoxazine colophonies, 0.1 weight part, 100 weight parts, 20 weight parts and the butanone solvent of 30 weight parts are mixed, are uniformly dispersed.
(3) semicure of resin combination and the preparation of substrate
By the performed polymer composition of above-mentioned epoxy resin modification polyphenylene oxide resin through with the impregnation of glass cloth after, 170 DEG C baking 3 minutes make prepreg, prepreg outward appearance enters shown in table one; Again two panels Copper Foil is coincided in obtained 4 prepreg both sides, adopt vacuum hotpressing machine, at temperature 190 DEG C, pressure 35kg/cm
2, under pressing time 90min condition, pressing and forming, to obtain a kind of copper foil laminates, performance test as shown in Table 2.
Embodiment three
(1) the prepolymer solution preparation of epoxy resin modification polyphenylene oxide resin:
By DCPD epoxy resin 20 parts and pyridine 0.005 part, dissolve in intensification and under stirring; Again by solid-state polyphenylene oxide resin 50 parts, be dissolved in toluene solvant and make the polyphenylene oxide resin solution that solid content is 30 ~ 70%, slowly be added dropwise in above-mentioned epoxy resin molten mass, after dropwising at 145 DEG C stirring reaction 6 hours and the prepolymer solution of epoxy resin modification polyphenylene oxide resin.Utilize in the molecular weight determination of GPC at the performed polymer of the epoxy resin modification polyphenylene oxide resin of gained, weight-average molecular weight is 6200.
(2) preparation of the performed polymer composition of epoxy resin modification polyphenylene oxide resin
The phosphonium flame retardant (PX-200, large eight chemistry of Japan) of the molten state silicon-dioxide of the 2-MI of the phenol novolacs of the performed polymer of step (1) the epoxy resin modification polyphenylene oxide resin of 60 weight parts, 20 weight parts, 40 weight part two amine type benzoxazine colophonies, 0.1 weight part, 100 weight parts, 20 weight parts and the butanone solvent of 30 weight parts are mixed, are uniformly dispersed.
(3) semicure of resin combination and the preparation of substrate
By the performed polymer composition of above-mentioned epoxy resin modification polyphenylene oxide resin through with the impregnation of glass cloth after, 170 DEG C baking 3 minutes make prepreg, prepreg outward appearance enters shown in table one; Again two panels Copper Foil is coincided in obtained 4 prepreg both sides, adopt vacuum hotpressing machine, at temperature 190 DEG C, pressure 35kg/cm
2, under pressing time 90min condition, pressing and forming, to obtain a kind of copper foil laminates, performance test as shown in Table 2.
Embodiment four
(1) the prepolymer solution preparation of epoxy resin modification polyphenylene oxide resin:
By DCPD epoxy resin 80 parts and pyridine 0.005 part, dissolve in intensification and under stirring; Again by solid-state polyphenylene oxide resin 50 parts, be dissolved in xylene solvent and make the polyphenylene oxide resin solution that solid content is 30 ~ 70%, slowly be added dropwise in above-mentioned epoxy resin molten mass, after dropwising at 145 DEG C stirring reaction 6 hours and the prepolymer solution of epoxy resin modification polyphenylene oxide resin.Utilize in the molecular weight determination of GPC at the performed polymer of the epoxy resin modification polyphenylene oxide resin of gained, weight-average molecular weight is 6600.
(2) preparation of the performed polymer composition of epoxy resin modification polyphenylene oxide resin
The phosphonium flame retardant (PX-200, large eight chemistry of Japan) of the molten state silicon-dioxide of the 2-MI of the phenol novolacs of the performed polymer of step (1) the epoxy resin modification polyphenylene oxide resin of 60 weight parts, 20 weight parts, 40 weight part two amine type benzoxazine colophonies, 0.1 weight part, 100 weight parts, 20 weight parts and the butanone solvent of 30 weight parts are mixed, are uniformly dispersed.
(3) semicure of resin combination and the preparation of substrate
By the performed polymer composition of above-mentioned epoxy resin modification polyphenylene oxide resin through with the impregnation of glass cloth after, 170 DEG C baking 3 minutes make prepreg, prepreg outward appearance enters shown in table one; Again two panels Copper Foil is coincided in obtained 4 prepreg both sides, adopt vacuum hotpressing machine, at temperature 190 DEG C, pressure 35kg/cm
2, under pressing time 90min condition, pressing and forming, to obtain a kind of copper foil laminates, performance test as shown in Table 2.
Embodiment five
(1) the prepolymer solution preparation of epoxy resin modification polyphenylene oxide resin:
By DCPD epoxy resin 50 parts and pyridine 0.005 part, dissolve in intensification and under stirring; Again by solid-state polyphenylene oxide resin 50 parts, be dissolved in xylene solvent and make the polyphenylene oxide resin solution that solid content is 30 ~ 70%, slowly be added dropwise in above-mentioned epoxy resin molten mass, after dropwising at 160 DEG C stirring reaction 6 hours and the prepolymer solution of epoxy resin modification polyphenylene oxide resin.
(2) preparation of the performed polymer composition of epoxy resin modification polyphenylene oxide resin
The phosphonium flame retardant (PX-200, large eight chemistry of Japan) of the molten state silicon-dioxide of the 2-MI of the phenol novolacs of the performed polymer of step (1) the epoxy resin modification polyphenylene oxide resin of 60 weight parts, 20 weight parts, 40 weight part two amine type benzoxazine colophonies, 0.1 weight part, 100 weight parts, 20 weight parts and the butanone solvent of 30 weight parts are mixed, are uniformly dispersed.Utilize in the molecular weight determination of GPC at the performed polymer of the epoxy resin modification polyphenylene oxide resin of gained, weight-average molecular weight is 6400.
(3) semicure of resin combination and the preparation of substrate
By the performed polymer composition of above-mentioned epoxy resin modification polyphenylene oxide resin through with the impregnation of glass cloth after, 170 DEG C baking 3 minutes make prepreg, prepreg outward appearance enters shown in table one; Again two panels Copper Foil is coincided in obtained 4 prepreg both sides, adopt vacuum hotpressing machine, at temperature 190 DEG C, pressure 35kg/cm
2, under pressing time 90min condition, pressing and forming, to obtain a kind of copper foil laminates, performance test as shown in Table 2.
Embodiment six
(1) the prepolymer solution preparation of epoxy resin modification polyphenylene oxide resin:
By DCPD epoxy resin 50 parts and pyridine 0.005 part, dissolve in intensification and under stirring; Again by solid-state polyphenylene oxide resin 50 parts, be dissolved in xylene solvent and make the polyphenylene oxide resin solution that solid content is 30 ~ 70%, slowly be added dropwise in above-mentioned epoxy resin molten mass, after dropwising at 125 DEG C stirring reaction 6 hours and the prepolymer solution of epoxy resin modification polyphenylene oxide resin.Utilize in the molecular weight determination of GPC at the performed polymer of the epoxy resin modification polyphenylene oxide resin of gained, weight-average molecular weight is 6150.
(2) preparation of the performed polymer composition of epoxy resin modification polyphenylene oxide resin
The phosphonium flame retardant (PX-200, large eight chemistry of Japan) of the molten state silicon-dioxide of the 2-MI of the phenol novolacs of the performed polymer of step (1) the epoxy resin modification polyphenylene oxide resin of 60 weight parts, 20 weight parts, 40 weight part two amine type benzoxazine colophonies, 0.1 weight part, 100 weight parts, 20 weight parts and the butanone solvent of 30 weight parts are mixed, are uniformly dispersed.
(3) semicure of resin combination and the preparation of substrate
By the performed polymer composition of above-mentioned epoxy resin modification polyphenylene oxide resin through with the impregnation of glass cloth after, 170 DEG C baking 3 minutes make prepreg, prepreg outward appearance enters shown in table one; Again two panels Copper Foil is coincided in obtained 4 prepreg both sides, adopt vacuum hotpressing machine, at temperature 190 DEG C, pressure 35kg/cm
2, under pressing time 90min condition, pressing and forming, to obtain a kind of copper foil laminates, performance test as shown in Table 2.
Embodiment seven
(1) the prepolymer solution preparation of epoxy resin modification polyphenylene oxide resin:
By bisphenol A type epoxy resin 50 parts and the vitriol oil 0.005 part, dissolve in intensification and under stirring; Again by solid-state polyphenylene oxide resin 50 parts, be dissolved in xylene solvent and make the polyphenylene oxide resin solution that solid content is 30 ~ 70%, slowly be added dropwise in above-mentioned epoxy resin molten mass, after dropwising at 145 DEG C stirring reaction 6 hours and epoxy resin modification polyphenylene oxide resin prepolymer solution.Utilize in the molecular weight determination of GPC at the performed polymer of the epoxy resin modification polyphenylene oxide resin of gained, weight-average molecular weight is 5700.
(2) preparation of the performed polymer composition of epoxy resin modification polyphenylene oxide resin
The phosphonium flame retardant (PX-200, large eight chemistry of Japan) of the molten state silicon-dioxide of the 2-MI of the phenol novolacs of the performed polymer of step (1) the epoxy resin modification polyphenylene oxide resin of 60 weight parts, 20 weight parts, 40 parts by weight of bisphenol A type benzoxazine colophonies, 0.1 weight part, 100 weight parts, 20 weight parts and the butanone solvent of 30 weight parts are mixed, are uniformly dispersed.
(3) semicure of resin combination and the preparation of substrate
By the performed polymer composition of above-mentioned epoxy resin modification polyphenylene oxide resin through with the impregnation of glass cloth after, 170 DEG C baking 3 minutes make prepreg, prepreg outward appearance enters shown in table one; Again two panels Copper Foil is coincided in obtained 4 prepreg both sides, adopt vacuum hotpressing machine, at temperature 190 DEG C, pressure 35kg/cm
2, under pressing time 90min condition, pressing and forming, to obtain a kind of copper foil laminates, performance test as shown in Table 2.
Embodiment eight
(1) the prepolymer solution preparation of epoxy resin modification polyphenylene oxide resin:
By bisphenol A type epoxy resin 50 parts and 0.005 part of poly(oxyethylene glycol) 400, dissolve in intensification and under stirring; Again by solid-state polyphenylene oxide resin 50 parts, be dissolved in toluene solvant and make the polyphenylene oxide resin solution that solid content is 30 ~ 70%, slowly be added dropwise in above-mentioned epoxy resin molten mass, after dropwising at 145 DEG C stirring reaction 6 hours and epoxy resin modification polyphenylene oxide resin prepolymer solution.Utilize in the molecular weight determination of GPC at the performed polymer of the epoxy resin modification polyphenylene oxide resin of gained, weight-average molecular weight is 5600.
(2) preparation of the performed polymer composition of epoxy resin modification polyphenylene oxide resin
The performed polymer of step (1) the epoxy resin modification polyphenylene oxide resin of 60 weight parts, 20 weight parts are starved phenol novolacs, 40 parts by weight of bisphenol A type benzoxazine colophonies, the 2-MI of 0.1 weight part, the molten state silicon-dioxide of 100 weight parts, the phosphonium flame retardant (PX-200, large eight chemistry of Japan) of 20 weight parts and the butanone solvent of 30 weight parts to mix, be uniformly dispersed.
(3) semicure of resin combination and the preparation of substrate
By the performed polymer composition of above-mentioned epoxy resin modification polyphenylene oxide resin through with the impregnation of glass cloth after, 170 DEG C baking 3 minutes make prepreg, prepreg outward appearance enters shown in table one; Again two panels Copper Foil is coincided in obtained 4 prepreg both sides, adopt vacuum hotpressing machine, at temperature 190 DEG C, pressure 35kg/cm
2, under pressing time 90min condition, pressing and forming, to obtain a kind of copper foil laminates, performance test as shown in Table 2.
Embodiment nine
(1) the prepolymer solution preparation of epoxy resin modification polyphenylene oxide resin:
By xenyl aralkyl type phenol novolac epoxy resins 50 parts and pyridine 0.005 part, dissolve in intensification and under stirring; Again by solid-state polyphenylene oxide resin 50 parts, be dissolved in toluene solvant and make the polyphenylene oxide resin solution that solid content is 30 ~ 70%, slowly be added dropwise in above-mentioned epoxy resin molten mass, after dropwising at 145 DEG C stirring reaction 6 hours and epoxy resin modification polyphenylene oxide resin prepolymer solution.
(2) preparation of the performed polymer composition of epoxy resin modification polyphenylene oxide resin
The phosphonium flame retardant (PX-200, large eight chemistry of Japan) of the molten state silicon-dioxide of the 2-MI of the phenol novolacs of the performed polymer of step (1) the epoxy resin modification polyphenylene oxide resin of 60 weight parts, 20 weight parts, 40 weight part two amine type benzoxazine colophonies, 0.1 weight part, 100 weight parts, 20 weight parts and the butanone solvent of 30 weight parts are mixed, are uniformly dispersed.
(3) semicure of resin combination and the preparation of substrate
By the performed polymer composition of above-mentioned epoxy resin modification polyphenylene oxide resin through with the impregnation of glass cloth after, 170 DEG C baking 3 minutes make prepreg, prepreg outward appearance enters shown in table one; Again two panels Copper Foil is coincided in obtained 4 prepreg both sides, adopt vacuum hotpressing machine, at temperature 190 DEG C, pressure 35kg/cm
2, under pressing time 90min condition, pressing and forming, to obtain a kind of copper foil laminates, performance test as shown in Table 2.
Comparative example one
(1) the prepolymer solution preparation of epoxy resin modification polyphenylene oxide resin:
Solid-state for the PPO of 100 weight parts polyphenylene oxide resin is added in butanone solvent, the liquid polyphenylene oxide resin solution of melt into, again by the glyoxal ethyline (2-methylimidazole of the bisphenol A type epoxy resin of 24 weight parts and 0.05 weight part, 2-MI), add in butanone solution, be uniformly mixed at 120 DEG C 1-3 hour and the solution arrived.The solution body of gained utilizes in the molecular weight determination of GPC, and weight-average molecular weight is 4000.
(2) preparation of the performed polymer composition of epoxy resin modification polyphenylene oxide resin
The phosphonium flame retardant (PX-200, large eight chemistry of Japan) of the molten state silicon-dioxide of the 2-MI of the phenol novolacs of the performed polymer of step (1) the epoxy resin modification polyphenylene oxide resin of 60 weight parts, 20 weight parts, 40 parts by weight of bisphenol A type benzoxazine colophonies, 0.1 weight part, 100 weight parts, 20 weight parts and the butanone solvent of 30 weight parts are mixed, are uniformly dispersed.
(3) semicure of resin combination and the preparation of substrate
By the performed polymer composition of above-mentioned epoxy resin modification polyphenylene oxide resin through with the impregnation of glass cloth after, 170 DEG C baking 3 minutes make prepreg, prepreg outward appearance enters shown in table one; Again two panels Copper Foil is coincided in obtained 4 prepreg both sides, adopt vacuum hotpressing machine, at temperature 190 DEG C, pressure 35kg/cm
2, under pressing time 90min condition, pressing and forming, to obtain a kind of copper foil laminates, performance test as shown in Table 3.
Comparative example two
(1) the prepolymer solution preparation of epoxy resin modification polyphenylene oxide resin:
By DCPD epoxy resin 50 parts and pyridine 0.005 part, dissolve in intensification and under stirring; Again by solid-state polyphenylene oxide resin 50 parts, be dissolved in xylene solvent and make the polyphenylene oxide resin solution that solid content is 30 ~ 70%, slowly be added dropwise in above-mentioned epoxy resin molten mass, after dropwising at 100-120 DEG C stirring reaction 6 hours and epoxy resin modification polyphenylene oxide resin prepolymer solution.Utilize in the molecular weight determination of GPC at the performed polymer of the epoxy resin modification polyphenylene oxide resin of gained, weight-average molecular weight is 4000.
(2) preparation of the performed polymer composition of epoxy resin modification polyphenylene oxide resin
The phosphonium flame retardant (PX-200, large eight chemistry of Japan) of the molten state silicon-dioxide of the 2-MI of the phenol novolacs of the performed polymer of step (1) the epoxy resin modification polyphenylene oxide resin of 60 weight parts, 20 weight parts, 40 parts by weight of bisphenol A type benzoxazine colophonies, 0.1 weight part, 100 weight parts, 20 weight parts and the butanone solvent of 30 weight parts are mixed, are uniformly dispersed.
(3) semicure of resin combination and the preparation of substrate
By the performed polymer composition of above-mentioned epoxy resin modification polyphenylene oxide resin through with the impregnation of glass cloth after, 170 DEG C baking 3 minutes make prepreg, prepreg outward appearance enters shown in table one; Again two panels Copper Foil is coincided in obtained 4 prepreg both sides, adopt vacuum hotpressing machine, at temperature 190 DEG C, pressure 35kg/cm
2, under pressing time 90min condition, pressing and forming, to obtain a kind of copper foil laminates, performance test as shown in Table 3.
Comparative example three
(1) the prepolymer solution preparation of epoxy resin modification polyphenylene oxide resin:
By DCPD epoxy resin 50 parts and pyridine 0.005 part, dissolve in intensification and under stirring; Again by solid-state polyphenylene oxide resin 50 parts, be dissolved in xylene solvent and make the polyphenylene oxide resin solution that solid content is 30 ~ 70%, slowly be added dropwise in above-mentioned epoxy resin molten mass, after dropwising at 145 DEG C stirring reaction 1-3 hour and epoxy resin modification polyphenylene oxide resin prepolymer solution.Utilize in the molecular weight determination of GPC at the performed polymer of the epoxy resin modification polyphenylene oxide resin of gained, weight-average molecular weight is 4500.
(2) preparation of the performed polymer composition of epoxy resin modification polyphenylene oxide resin
The phosphonium flame retardant (PX-200, large eight chemistry of Japan) of the molten state silicon-dioxide of the 2-MI of the phenol novolacs of the performed polymer of step (1) the epoxy resin modification polyphenylene oxide resin of 60 weight parts, 20 weight parts, 100 weight part two amine type benzoxazine colophonies, 0.1 weight part, 100 weight parts, 20 weight parts and the butanone solvent of 30 weight parts are mixed, are uniformly dispersed.
(3) semicure of resin combination and the preparation of substrate
By the performed polymer composition of above-mentioned epoxy resin modification polyphenylene oxide resin through with the impregnation of glass cloth after, within 3 minutes, make prepreg prepreg outward appearance 170 DEG C of bakings and enter shown in table one; Again two panels Copper Foil is coincided in obtained 4 prepreg both sides, adopt vacuum hotpressing machine, at temperature 190 DEG C, pressure 35kg/cm
2, under pressing time 90min condition, pressing and forming, to obtain a kind of copper foil laminates, wherein semicure film solidify to form the insulation layer between two Copper Foils, and performance test as shown in Table 3.
Comparative example four
(1) preparation of epoxy resin and benzoxazine colophony composition
The phosphonium flame retardant (PX-200, large eight chemistry of Japan) of the molten state silicon-dioxide of the 2-MI of the phenol novolacs of 20 weight parts, 100 weight part two amine type benzoxazine colophonies, 0.1 weight part, 100 weight parts, 20 weight parts and the butanone solvent of 30 weight parts are mixed, are uniformly dispersed.
(2) semicure of resin combination and the preparation of substrate
By above-mentioned epoxy resin and benzoxazine colophony composition through with the impregnation of glass cloth after, within 3 minutes, make prepreg 170 DEG C of bakings, prepreg outward appearance enters shown in table one; Again two panels Copper Foil is coincided in obtained 4 prepreg both sides, adopt vacuum hotpressing machine, at temperature 190 DEG C, pressure 35kg/cm
2, under pressing time 90min condition, pressing and forming, to obtain a kind of copper foil laminates, wherein semicure film solidify to form the insulation layer between two Copper Foils, and performance test as shown in Table 3.
Comparative example five
(1) preparation of epoxy resin, benzoxazine colophony and unmodified polyphenyl ether resin composition
The phosphonium flame retardant (PX-200, large eight chemistry of Japan) of the molten state silicon-dioxide of the 2-MI of the phenol novolacs of the unmodified polyphenylene oxide resin of 60 weight parts, 20 weight parts, 100 weight part two amine type benzoxazine colophonies, 0.1 weight part, 100 weight parts, 20 weight parts and the butanone solvent of 30 weight parts are mixed, are uniformly dispersed.
(2) semicure of resin combination and the preparation of substrate
Epoxy resin, benzoxazine colophony and unmodified polyphenyl ether resin composition through with the impregnation of glass cloth after, 170 DEG C baking 3 minutes make prepreg, prepreg outward appearance enters shown in table one; Again two panels Copper Foil is coincided in obtained 4 prepreg both sides, adopt vacuum hotpressing machine, at temperature 190 DEG C, pressure 35kg/cm
2, under pressing time 90min condition, pressing and forming, to obtain a kind of copper foil laminates, wherein semicure film solidify to form the insulation layer between two Copper Foils, and performance test as shown in Table 3.
The prepreg of embodiment one to nine and comparative example one to five gained is observed its outward appearance and recorded as shown in Table 1, and the prepreg outward appearance of result display embodiment one to nine is more smooth, and air entrapment amount is less.The prepreg outward appearance of comparative example one to five is then very coarse, and when glass is distributed in impregnation, surface can film forming, and cause impregnation bad, the polyphenylene oxide resin of the epoxide functional groups modification that display the present invention discloses effectively can improve the wetting property of prepreg.
Table one prepreg outward appearance
The laminated wood of embodiment one to nine gained carries out characteristic test data as shown in Table 2, and the laminated wood of comparative example one to five gained carries out characteristic test data as shown in Table 3.Embodiment result shows that the preparation method of epoxide modified polyphenylene oxide resin of the present invention is in the ratio (embodiment two to four) using different epoxy resin (embodiment one, two and nine), different epoxy resin and polyphenylene oxide resin, and at temperature of reaction 125-160 of the present invention DEG C, (embodiment two, five and six) and different catalysts kind (embodiment one, seven and eight) can obtain desirable epoxy Noryl prepolymer.Compared with the resin combination (comparative example four) not containing epoxide modified polyphenylene oxide resin or resin combination (comparative example five) the gained sheet material containing unmodified polyphenylene oxide resin, resin combination gained sheet material containing the epoxy resin modification polyphenylene oxide resin disclosed by the present invention has better dielectric properties (Dk/Df) and Tg (glass transition temp), wherein Dk and Df value is lower is preferably electrical property, and Tg temperature is higher is preferably Tg.
The result of comparative example one shows to utilize imidazoles as catalyzer, temperature of reaction 100-120 DEG C, reaction times be 1-3 hour not polyphenylene ether resin play modified effect, in time extend the reaction times to 6 hour (comparative example two), effect is also and not obvious.When temperature is elevated to 145 DEG C, dielectric properties and the Tg of the veneer sheet containing this resin prepolymer are significantly improved, but because the reaction times is too short, the hydroxyl reaction of epoxide group and polyphenylene oxide resin is insufficient, and thus gained plate property is well below the sheet material (embodiment one to nine) reacting the performed polymer gained under 6 hours conditions at 145 DEG C.In addition, comparative example one, two and comparative example four, five gained plate property are more or less the same, and also illustrate that at 100-120 DEG C, react 1-3 hour polyphenylene ether resin does not play effective modifying function.
Therefore, the method for the epoxide modified polyphenylene oxide resin of preparation provided by the invention, and the sheet material of the resin combination gained containing this epoxide modified polyphenylene oxide resin and benzoxazine colophony has wide range of applications, and has larger productive value.
Table two example composition veneer sheet characteristic
Table three comparative example composition layer pressing plate characteristic
| Performance | Comparative example one | Comparative example two | Comparative example three | Comparative example four | Comparative example five |
| Tg(DSC)/℃ | 144 | 145 | 159 | 154 | 146 |
| Stripping 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 |
| DK1G | 4.38 | 4.35 | 4.26 | 4.40 | 4.32 |
| Df1G | 0.013 | 0.013 | 0.010 | 0.012 | 0.012 |
Applicant states, the present invention illustrates method detailed of the present invention by above-described embodiment, but the present invention is not limited to above-mentioned method detailed, does not namely mean that the present invention must rely on above-mentioned method detailed and could implement.Person of ordinary skill in the field should understand, any improvement in the present invention, to equivalence replacement and the interpolation of ancillary component, the concrete way choice etc. of each raw material of product of the present invention, all drops within protection scope of the present invention and open scope.
Claims (10)
1. a resin combination, this resin combination comprises performed polymer and the benzoxazine colophony of epoxy resin modification polyphenylene oxide resin.
2. resin combination as claimed in claim 1, it is characterized in that, the performed polymer of described epoxy resin modification polyphenylene oxide resin has the structure as shown in formula I:
Wherein, X is:
Wherein, R is alkylidene group, the singly-bound ,-SO of substituted or unsubstituted C1 ~ C5
2-,-O-,-CO-,-SO-or-SC-;
Y is the functional group of functional epoxy resin;
Z
1, Z
2, Z
3, Z
4identical or different, be the alkyl or phenyl of hydrogen atom, halogen atom, carbonatoms less than 8 all independently;
N be greater than 1 positive integer;
Preferably, in formula I, X is
Preferably, described polyphenylene oxide resin molecular structure is as shown in formula II:
Wherein, X is:
Wherein, R is alkylidene group, the singly-bound ,-SO of substituted or unsubstituted C1 ~ C5
2-,-O-,-CO-,-SO-or-SC-;
Z
1, Z
2, Z
3, Z
4identical or different, be the alkyl or phenyl of hydrogen atom, halogen atom, carbonatoms less than 8 all independently;
N be greater than 1 positive integer;
Preferably, the X in formula II is:
Preferably, the molecular structural formula of described polyphenylene oxide resin is such as formula shown in (III) or formula (IV):
N be greater than 1 positive integer;
Preferably, described functional 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, Study On O-cresol Epoxy Resin, trifunctional base epoxy, four functional group's epoxy resin, Dicyclopentadiene (DCPD) epoxy resin, p-aminophenol epoxy resin, tricyanic epoxy resin, phosphorous epoxy resin, nitrogen-containing epoxy thermoset, p-Xylol epoxy resin, naphthalene type epoxy resin, benzo croak is muttered type epoxy resin, the mixture of any one or at least two kinds in xenol formaldehyde epoxy resin or phenolic group benzene alkyl phenolic epoxy resin,
Preferably, in formula (I), Y is any one in following structure:
Wherein, the positive integer of m and n all independently for being greater than 1.
3. resin combination as claimed in claim 1 or 2, it is characterized in that, the performed polymer of described epoxy resin modification polyphenylene oxide resin is reacted as follows by solid-state polyphenylene oxide resin and epoxy resin and obtained:
By epoxy resin 20-80 weight part and catalyzer 0.005 ~ 10 weight part, dissolve in intensification and under stirring; Again by solid-state polyphenylene oxide resin 50 weight part, be dissolved in organic solvent and make the polyphenylene oxide resin solution that solid content is 30 ~ 70%, then it is slowly added dropwise in above-mentioned epoxy resin molten mass, after dropwising at 125 ~ 160 DEG C stirring reaction 3.5-12 hour, the prepolymer solution of obtained epoxy resin modification polyphenylene oxide resin.
4. resin combination as claimed in claim 3, it is characterized in that, the addition of epoxy resin is 30 ~ 70 weight parts, is preferably 40 ~ 60 weight parts;
Preferably, the addition of catalyzer is 0.005 ~ 5 weight part, preferably 0.005 ~ 1 weight part;
Preferably, described catalyzer is the mixture of any one or at least two kinds in polyethers, cyclic crown ether class, amine, inorganic strong alkali or inorganic acid;
Preferably, described polyethers is that chain polyoxyethylene glycol is or/and chain dialkylethers;
Preferably, described cyclic crown ether class is the mixture that 18 hats 6,15 are preced with any one or at least two kinds in 5 or cyclodextrin etc.;
Preferably, described amine is the mixture of any one or at least two kinds in quaternary ammonium salt, tertiary amine or pyridine compounds;
Preferably, described quaternary ammonium salt is the mixture of any one or at least two kinds in benzyltriethylammoinium chloride, Tetrabutyl amonium bromide, tetrabutylammonium chloride, 4-butyl ammonium hydrogen sulfate, tri-n-octyl methyl ammonium chloride, Dodecyl trimethyl ammonium chloride or tetradecyl trimethyl ammonium chloride etc.;
Preferably, described tertiary amine is R
3n, wherein R be the branched-chain or straight-chain alkyl of carbonatoms less than 18, replacement or the phenyl that do not replace, the mixture of any one or at least two kinds in preferred triethylamine, Tributylamine, dioctylmethylamine or phenylbenzene methylamine etc.;
Preferably, described pyridine compounds be pyridine, mixture with any one in less than 8 carbon atom side chains or the substituent pyridine of straight-chain paraffin, phenylpyridine or dipyridyl etc. or at least two kinds;
Preferably, described dipyridyl is 2,2 '-dipyridyl, 4,4'-Bipyridine, 2,4 '-dipyridyl or 2, the mixture of any one or at least two kinds in 3 '-dipyridyl;
Preferably, described inorganic strong alkali is that sodium hydroxide is or/and potassium hydroxide;
Preferably, described inorganic acid is the mixture of any one or at least two kinds in the vitriol oil, hydrochloric acid or nitric acid etc.;
Preferably, the temperature of described stirring reaction is 130-150 DEG C, and the time of stirring reaction is 4-8 hour;
Preferably, described organic solvent is the mixed solvent of any one or at least two kinds in DMF, N, N-diethylformamide, pimelinketone, toluene, dimethylbenzene, trimethylbenzene or durene.
5. the resin combination as described in one of claim 1-4, is characterized in that, in resin combination, the addition of the performed polymer of epoxy resin modification polyphenylene oxide resin is 20-80 weight part;
Preferably, in resin combination, the content of described benzoxazine colophony is 10-60 weight part;
Preferably, described benzoxazine colophony is the mixture of any one or at least two kinds in bisphenol A benzoxazine, Bisphenol F benzoxazine, bisphenol S benzoxazine, two amine type benzoxazines, phenolphthalein type benzoxazine or dicyclopentadiene-type benzoxazine.
6. the resin combination as described in one of claim 1-5, is characterized in that, also comprises solidifying agent in described resin combination, and its content is 5 ~ 50 weight parts;
Preferably, described solidifying agent is selected from any one or the two or more mixtures in linear phenolic resin, Zelan 338 resin, DDS or DDM;
Preferably, also comprise curing catalyst in described resin combination, its content is 0.01 ~ 10 weight part;
Preferably, described curing catalyst is selected from the lewis base of the combination of any one or at least two kinds in imidazoles, boron trifluoride amine compound, chlorination Yi base triphenyl phosphonium, glyoxal ethyline, 2-phenylimidazole, 2-ethyl-4-methylimidazole, triphenylphosphine or 4-dimethylaminopyridine, or be selected from the lewis acid of metal salt compound of any one or at least two kinds in manganese, iron, cobalt, nickel, copper or zinc, or be selected from organo-peroxide;
Preferably, described resin composition comprise further 5 ~ 60 weight parts without prepolymerized epoxy resin;
Preferably, described 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, Study On O-cresol Epoxy Resin, trifunctional base epoxy, four functional group's epoxy resin, Dicyclopentadiene (DCPD) epoxy resin, p-aminophenol epoxy resin, tricyanic epoxy resin, phosphorous epoxy resin, nitrogen-containing epoxy thermoset, brominated epoxy resin, p-Xylol epoxy resin, naphthalene type epoxy resin, benzo croak is muttered type epoxy resin, any one or two or more mixtures in xenol formaldehyde epoxy resin or phenolic group benzene alkyl phenolic epoxy resin,
Preferably, the mixture of any one or at least two kinds in mineral filler, fire retardant, interfacial agent, dispersion agent, silicone elastomer or toughner is comprised in described resin combination further.
7. a prepreg, it comprises strongthener and by the resin combination as described in claim 1-6 one of of the dry postadhesion of impregnation on strongthener.
8. a veneer sheet, described veneer sheet contains at least one prepreg as claimed in claim 7.
9. a copper-clad laminate, described copper-clad laminate comprises at least one superimposed prepreg as claimed in claim 7 and covers the Copper Foil of one or both sides of the prepreg after superimposed.
10. a printed wiring veneer sheet, it contains at least one prepreg as claimed in claim 7.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| 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 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510852434.9A CN105419348B (en) | 2016-01-18 | 2016-01-18 | A kind of resin combination and prepreg and laminate using it |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105419348A true CN105419348A (en) | 2016-03-23 |
| CN105419348B CN105419348B (en) | 2018-11-27 |
Family
ID=55497909
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510852434.9A Expired - Fee Related CN105419348B (en) | 2016-01-18 | 2016-01-18 | A kind of resin combination and prepreg and laminate using it |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN105419348B (en) |
| WO (1) | WO2017124668A1 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106832778A (en) * | 2017-02-13 | 2017-06-13 | 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 |
| WO2017124668A1 (en) * | 2016-01-18 | 2017-07-27 | 广东生益科技股份有限公司 | Resin composition, and prepreg and laminated board using same |
| CN107502261A (en) * | 2017-09-14 | 2017-12-22 | 广州欣凯化工科技有限公司 | A kind of freeze proof resin glue of high temperature resistant for woodwork |
| WO2018120589A1 (en) * | 2016-12-29 | 2018-07-05 | 广东生益科技股份有限公司 | Modified polyphenylene ether resin and application thereof |
| CN114804893A (en) * | 2022-05-17 | 2022-07-29 | 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 |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100402582C (en) * | 2001-09-20 | 2008-07-16 | 旭化成化学株式会社 | Functionalized polyphenylene ether |
| CN102093666A (en) * | 2010-12-23 | 2011-06-15 | 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 |
| WO2014104743A1 (en) * | 2012-12-26 | 2014-07-03 | 주식회사 두산 | Resin composition and metal foil laminate comprising same |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| US7439310B2 (en) * | 2006-07-06 | 2008-10-21 | Asahi Kasei Chemicals Corporation | Polyphenylene ether modified by reaction with cresol novolac epoxy resin |
| 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 |
| 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 |
-
2016
- 2016-01-18 CN CN201510852434.9A patent/CN105419348B/en not_active Expired - Fee Related
- 2016-05-13 WO PCT/CN2016/082107 patent/WO2017124668A1/en active Application Filing
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100402582C (en) * | 2001-09-20 | 2008-07-16 | 旭化成化学株式会社 | Functionalized polyphenylene ether |
| CN102093666A (en) * | 2010-12-23 | 2011-06-15 | 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 |
| WO2014104743A1 (en) * | 2012-12-26 | 2014-07-03 | 주식회사 두산 | Resin composition and metal foil laminate comprising same |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017124668A1 (en) * | 2016-01-18 | 2017-07-27 | 广东生益科技股份有限公司 | Resin composition, and prepreg and laminated board using same |
| WO2018120589A1 (en) * | 2016-12-29 | 2018-07-05 | 广东生益科技股份有限公司 | Modified polyphenylene ether resin and application thereof |
| CN106832778A (en) * | 2017-02-13 | 2017-06-13 | 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 |
| 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 |
| CN107502261A (en) * | 2017-09-14 | 2017-12-22 | 广州欣凯化工科技有限公司 | A kind of freeze proof resin glue of high temperature resistant for woodwork |
| 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 |
| CN114804893A (en) * | 2022-05-17 | 2022-07-29 | 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2017124668A1 (en) | 2017-07-27 |
| CN105419348B (en) | 2018-11-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105419348A (en) | Resin composition and presoaking material and laminated board using same | |
| CN101240111B (en) | Prepreg and laminate | |
| CN101796132B (en) | Epoxy resin composition, prepreg using the epoxy resin composition, metal-clad laminate, and printed wiring board | |
| CN102807658B (en) | Polyphenyl ether resin composite and prepreg and copper clad laminate made of polyphenyl ether resin composite | |
| CN102838864B (en) | Resin composition and prepreg and laminate manufactured by using same | |
| JP5264133B2 (en) | Epoxy resin composition, prepreg and metal-clad laminate using the epoxy resin composition | |
| CN104508005A (en) | Modified polyphenylene ether, method for manufacturing same, polyphenylene ether resin composition, resin varnish, prepreg, metal-clad laminate and printed circuit board | |
| CN104968725A (en) | Resin composition, resin varnish, prepreg, metal-clad laminate and printed wiring board | |
| CN102115600A (en) | Thermosetting resin composition, prepreg and laminated board | |
| CN103189418A (en) | Process for producing compatibilized resin, thermosetting resin composition, prepreg, and laminate | |
| CN102558759B (en) | Cyanate ester resin composition and prepreg and laminated material manufactured by using same | |
| CN103992622A (en) | Halogen-free resin composition, prepreg prepared from halogen-free resin composition and laminated board prepared from halogen-free resin composition and used for printed circuit | |
| CN105331053A (en) | Halogen-free resin composition, and prepreg and laminated board for printed circuit prepared from the resin composition | |
| EP3392286B1 (en) | Epoxy resin composition and prepreg, laminated board and printed-circuit board comprising same | |
| TWI588204B (en) | An epoxy resin composition and a prepreg and a laminate using the same | |
| TWI494370B (en) | Epoxy group-modified polyphenylene ether resin, resin composition and application thereof | |
| CN105131597A (en) | Halogen-free resin composition and prepreg using halogen-free resin composition and printed circuit laminated board | |
| KR101828762B1 (en) | Thermosetting resin composition and its production method, prepreg, laminate, and printed wiring board | |
| CN108602318A (en) | Metal-clad, the manufacturing method of metal-clad, the metal component of resin, resin metal component manufacturing method, the manufacturing method of wiring plate and wiring plate | |
| CN103833873A (en) | Epoxy modified maleic anhydride copolymer prepolymer, its resin composition, preparation method and application | |
| CN109439257A (en) | A kind of preparation method of the low dielectric type copper coated foil plate of the high Tg of Halogen | |
| JP5793640B2 (en) | Epoxy resin composition for printed wiring board, prepreg for printed wiring board using the epoxy resin composition for printed wiring board, and metal-clad laminate for printed wiring board | |
| JP5919576B2 (en) | Epoxy resin composition for printed wiring board, prepreg for printed wiring board using the epoxy resin composition for printed wiring board, and metal-clad laminate for printed wiring board | |
| JP6664092B2 (en) | Resin composition, resin varnish, prepreg, metal-clad laminate, and printed wiring board | |
| TWI763282B (en) | A halogen-free flame retardant resin composition and its application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20181127 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |