WO2022134231A1 - Halogen-free flame-retardant resin composition and application thereof - Google Patents
Halogen-free flame-retardant resin composition and application thereof Download PDFInfo
- Publication number
- WO2022134231A1 WO2022134231A1 PCT/CN2021/070910 CN2021070910W WO2022134231A1 WO 2022134231 A1 WO2022134231 A1 WO 2022134231A1 CN 2021070910 W CN2021070910 W CN 2021070910W WO 2022134231 A1 WO2022134231 A1 WO 2022134231A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- resin
- resin composition
- weight
- parts
- halogen
- Prior art date
Links
- 239000011342 resin composition Substances 0.000 title claims abstract description 74
- 239000003063 flame retardant Substances 0.000 title claims abstract description 39
- 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 title claims abstract description 15
- 229920005989 resin Polymers 0.000 claims abstract description 101
- 239000011347 resin Substances 0.000 claims abstract description 101
- -1 maleimide compound Chemical class 0.000 claims abstract description 52
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000011574 phosphorus Substances 0.000 claims abstract description 45
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 45
- CMLFRMDBDNHMRA-UHFFFAOYSA-N 2h-1,2-benzoxazine Chemical compound C1=CC=C2C=CNOC2=C1 CMLFRMDBDNHMRA-UHFFFAOYSA-N 0.000 claims abstract description 43
- 239000003822 epoxy resin Substances 0.000 claims abstract description 43
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 43
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000011889 copper foil Substances 0.000 claims abstract description 9
- 229910052751 metal Inorganic materials 0.000 claims abstract description 8
- 239000002184 metal Substances 0.000 claims abstract description 8
- 239000007787 solid Substances 0.000 claims abstract description 4
- 239000000463 material Substances 0.000 claims description 22
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 claims description 19
- 229920001955 polyphenylene ether Polymers 0.000 claims description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- 150000002148 esters Chemical class 0.000 claims description 13
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 9
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 8
- 239000000945 filler Substances 0.000 claims description 8
- 239000011888 foil Substances 0.000 claims description 8
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000000654 additive Substances 0.000 claims description 6
- 230000000996 additive effect Effects 0.000 claims description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-M acrylate group Chemical group C(C=C)(=O)[O-] NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- 125000001624 naphthyl group Chemical group 0.000 claims description 5
- 125000005504 styryl group Chemical group 0.000 claims description 5
- IPJGAEWUPXWFPL-UHFFFAOYSA-N 1-[3-(2,5-dioxopyrrol-1-yl)phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC(N2C(C=CC2=O)=O)=C1 IPJGAEWUPXWFPL-UHFFFAOYSA-N 0.000 claims description 4
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 claims description 4
- 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 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
- 150000001412 amines Chemical class 0.000 claims description 4
- 239000004305 biphenyl Substances 0.000 claims description 4
- 235000010290 biphenyl Nutrition 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 3
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 claims description 3
- 239000005062 Polybutadiene Substances 0.000 claims description 3
- 125000001931 aliphatic group Chemical group 0.000 claims description 3
- 239000004841 bisphenol A epoxy resin Substances 0.000 claims description 3
- 238000005470 impregnation Methods 0.000 claims description 3
- 239000004843 novolac epoxy resin Substances 0.000 claims description 3
- NAKOELLGRBLZOF-UHFFFAOYSA-N phenoxybenzene;pyrrole-2,5-dione Chemical compound O=C1NC(=O)C=C1.O=C1NC(=O)C=C1.C=1C=CC=CC=1OC1=CC=CC=C1 NAKOELLGRBLZOF-UHFFFAOYSA-N 0.000 claims description 3
- 150000003017 phosphorus Chemical class 0.000 claims description 3
- 229920002857 polybutadiene Polymers 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 3
- OWICEWMBIBPFAH-UHFFFAOYSA-N (3-diphenoxyphosphoryloxyphenyl) diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=C(OP(=O)(OC=2C=CC=CC=2)OC=2C=CC=CC=2)C=CC=1)(=O)OC1=CC=CC=C1 OWICEWMBIBPFAH-UHFFFAOYSA-N 0.000 claims description 2
- NOQJZCJOXLFFCH-UHFFFAOYSA-N 3-(2,3-dimethylphenyl)pyrrole-2,5-dione Chemical compound CC1=CC=CC(C=2C(NC(=O)C=2)=O)=C1C NOQJZCJOXLFFCH-UHFFFAOYSA-N 0.000 claims description 2
- MOSSLXZUUKTULI-UHFFFAOYSA-N 3-[3-(2,5-dioxopyrrol-3-yl)-4-methylphenyl]pyrrole-2,5-dione Chemical compound CC1=CC=C(C=2C(NC(=O)C=2)=O)C=C1C1=CC(=O)NC1=O MOSSLXZUUKTULI-UHFFFAOYSA-N 0.000 claims description 2
- 125000006374 C2-C10 alkenyl group Chemical group 0.000 claims description 2
- 239000002841 Lewis acid Chemical class 0.000 claims description 2
- 229910021536 Zeolite Inorganic materials 0.000 claims description 2
- BQPNUOYXSVUVMY-UHFFFAOYSA-N [4-[2-(4-diphenoxyphosphoryloxyphenyl)propan-2-yl]phenyl] diphenyl phosphate Chemical compound C=1C=C(OP(=O)(OC=2C=CC=CC=2)OC=2C=CC=CC=2)C=CC=1C(C)(C)C(C=C1)=CC=C1OP(=O)(OC=1C=CC=CC=1)OC1=CC=CC=C1 BQPNUOYXSVUVMY-UHFFFAOYSA-N 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 125000004104 aryloxy group Chemical group 0.000 claims description 2
- 229910001593 boehmite Inorganic materials 0.000 claims description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- 239000000378 calcium silicate Substances 0.000 claims description 2
- 229910052918 calcium silicate Inorganic materials 0.000 claims description 2
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 claims description 2
- 239000004927 clay Substances 0.000 claims description 2
- 229910052570 clay Inorganic materials 0.000 claims description 2
- 239000004643 cyanate ester Chemical class 0.000 claims description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 2
- 230000002209 hydrophobic effect Effects 0.000 claims description 2
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 2
- 239000012948 isocyanate Substances 0.000 claims description 2
- 150000002513 isocyanates Chemical class 0.000 claims description 2
- 150000007517 lewis acids Chemical class 0.000 claims description 2
- 239000000395 magnesium oxide Substances 0.000 claims description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 2
- 239000010445 mica Substances 0.000 claims description 2
- 229910052618 mica group Inorganic materials 0.000 claims description 2
- 150000002989 phenols Chemical class 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 150000003222 pyridines Chemical class 0.000 claims description 2
- 239000004575 stone Substances 0.000 claims description 2
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 claims description 2
- KOWVWXQNQNCRRS-UHFFFAOYSA-N tris(2,4-dimethylphenyl) phosphate Chemical compound CC1=CC(C)=CC=C1OP(=O)(OC=1C(=CC(C)=CC=1)C)OC1=CC=C(C)C=C1C KOWVWXQNQNCRRS-UHFFFAOYSA-N 0.000 claims description 2
- 229920002554 vinyl polymer Polymers 0.000 claims description 2
- 239000010456 wollastonite Substances 0.000 claims description 2
- 229910052882 wollastonite Inorganic materials 0.000 claims description 2
- 239000010457 zeolite Substances 0.000 claims description 2
- PPQRFOFHENJYMN-UHFFFAOYSA-N 3-(2,6-dimethylphenyl)pyrrole-2,5-dione Chemical compound CC1=CC=CC(C)=C1C1=CC(=O)NC1=O PPQRFOFHENJYMN-UHFFFAOYSA-N 0.000 claims 1
- 229930185605 Bisphenol Natural products 0.000 claims 1
- 239000002253 acid Substances 0.000 claims 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims 1
- 229920003192 poly(bis maleimide) Polymers 0.000 claims 1
- 239000000203 mixture Substances 0.000 abstract description 8
- 238000000034 method Methods 0.000 description 20
- 238000002360 preparation method Methods 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 11
- 238000012360 testing method Methods 0.000 description 11
- 230000008569 process Effects 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 150000003923 2,5-pyrrolediones Chemical class 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- VVJKKWFAADXIJK-UHFFFAOYSA-N Allylamine Chemical compound NCC=C VVJKKWFAADXIJK-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 230000035939 shock Effects 0.000 description 6
- 238000004132 cross linking Methods 0.000 description 5
- 239000004593 Epoxy Substances 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 230000032798 delamination Effects 0.000 description 4
- 239000004744 fabric Substances 0.000 description 4
- 230000009477 glass transition Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- XKZQKPRCPNGNFR-UHFFFAOYSA-N 2-(3-hydroxyphenyl)phenol Chemical group OC1=CC=CC(C=2C(=CC=CC=2)O)=C1 XKZQKPRCPNGNFR-UHFFFAOYSA-N 0.000 description 3
- BCHZICNRHXRCHY-UHFFFAOYSA-N 2h-oxazine Chemical group N1OC=CC=C1 BCHZICNRHXRCHY-UHFFFAOYSA-N 0.000 description 3
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 239000005457 ice water Substances 0.000 description 3
- 229920003986 novolac Polymers 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000013112 stability test Methods 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000005587 bubbling Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000010382 chemical cross-linking Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- HIDBROSJWZYGSZ-UHFFFAOYSA-N 1-phenylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC=C1 HIDBROSJWZYGSZ-UHFFFAOYSA-N 0.000 description 1
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 1
- 229920006310 Asahi-Kasei Polymers 0.000 description 1
- HECLRDQVFMWTQS-UHFFFAOYSA-N Dicyclopentadiene Chemical compound C1C2C3CC=CC3C1C=C2 HECLRDQVFMWTQS-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- NHADDZMCASKINP-HTRCEHHLSA-N decarboxydihydrocitrinin Natural products C1=C(O)C(C)=C2[C@H](C)[C@@H](C)OCC2=C1O NHADDZMCASKINP-HTRCEHHLSA-N 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 1
- 239000005007 epoxy-phenolic resin Substances 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012784 inorganic fiber Substances 0.000 description 1
- 125000005647 linker group Chemical group 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 125000005439 maleimidyl group Chemical group C1(C=CC(N1*)=O)=O 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- GKTNLYAAZKKMTQ-UHFFFAOYSA-N n-[bis(dimethylamino)phosphinimyl]-n-methylmethanamine Chemical compound CN(C)P(=N)(N(C)C)N(C)C GKTNLYAAZKKMTQ-UHFFFAOYSA-N 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- MPNNOLHYOHFJKL-UHFFFAOYSA-N peroxyphosphoric acid Chemical group OOP(O)(O)=O MPNNOLHYOHFJKL-UHFFFAOYSA-N 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000009774 resonance method Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
Classifications
-
- 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
- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08L79/085—Unsaturated polyimide precursors
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/14—Layered products comprising a layer of metal next to a fibrous or filamentary layer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- 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
-
- 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
- B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
- B32B17/067—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of fibres or filaments
-
- 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
- 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
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
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Definitions
- the invention relates to the technical field of laminates, in particular to a halogen-free flame retardant resin composition and its application.
- additive flame retardants such as condensed phosphate ester, phosphazene and their derivatives to achieve halogen-free flame retardant or low halogen flame retardant.
- the melting point or softening point of most additive flame retardants is low, which will significantly reduce the glass transition temperature of the resin system.
- the temperature exceeds a certain limit during processing especially when the glass transition temperature of the resin exceeds the glass transition temperature of the resin, the deformation of the substrate increases sharply. , the dimensional stability is greatly reduced.
- Some practitioners choose epoxy resins and phenolic resins containing phosphorus structures as flame retardant resins, but these resins are not satisfactory in terms of heat resistance, reliability and dielectric properties.
- low-polarity resin materials is easy to achieve low dielectric properties, but low-polarity materials tend to have poor rigidity or poor adhesion, and are prone to warpage and wire throwing during PCB (copper wire and substrate separation) Scrap and increase manufacturing costs.
- the present invention provides a halogen-free flame retardant resin composition and its application.
- the halogen-free flame retardant resin composition provided by the present invention effectively improves the dielectric properties of the resin composition while ensuring that it has high Tg and high heat resistance; It has excellent dimensional stability with excellent performance.
- the present invention provides a halogen-free flame retardant resin composition, in parts by weight of solid components, comprising the following components:
- the inventor found that by adding a phosphorus-containing benzoxazine resin component containing an unsaturated bond at the end group to the resin composition, (1) the oxazine ring can be opened at high temperature to form a hydroxyl group, which is compatible with epoxy resin.
- the effective crosslinking between the components solves the problem that the epoxy resin and the maleimide compound cannot react effectively, thereby obtaining better dielectric properties than the conventional benzoxazine.
- the phosphorus-containing benzoxazine resin component whose terminal group contains unsaturated bonds adopted in the present invention can effectively solve the problem of halogen-free flame retardant because of the phosphorus element in its molecular structure;
- the existence of the oxazine ring balances the drawbacks caused by the easy water absorption of phosphorus elements to the greatest extent, and effectively reduces the problem of water absorption of the board, thereby improving the dielectric stability and reliability of the resin composition.
- phosphorus-containing benzoxazine resins whose end groups contain unsaturated bonds can effectively ensure that phosphorus elements and the host resin are in a chemically cross-linked state, and prevent phosphorus elements from being free and easy to precipitate.
- the resin composition of the present invention due to the addition of the phosphorus-containing benzoxazine resin component containing an unsaturated bond at the end group, the phosphorus-containing group and the benzoxazine structure cooperate with each other, and at the same time solve the problem of Reactive flame retardants are prone to problems of increased water absorption, decreased dimensional stability, and decreased heat resistance.
- the phosphorus-containing benzoxazine resin component with unsaturated bond at the end group adopted in the present invention can provide more cross-linking due to the unsaturated bond in its molecular structure.
- the junction point reacts with the maleimide compound, it is easier to form a dense cross-linked network, and the dielectric constant and dielectric loss factor are effectively reduced.
- the content of the epoxy resin (A) is 1 to 40 parts by weight, for example, 1 part by weight, 2 parts by weight, 5 parts by weight, 10 parts by weight, 15 parts by weight, 20 parts by weight parts by weight, 25 parts by weight, 30 parts by weight, 35 parts by weight or 40 parts by weight, preferably 5 to 30 parts by weight.
- the content of the phosphorus-containing benzoxazine resin (B) whose terminal groups contain unsaturated bonds is 1 to 30 parts by weight, for example, 1 part by weight, 2 parts by weight, 5 parts by weight part, 10 parts by weight, 15 parts by weight, 20 parts by weight, 25 parts by weight or 30 parts by weight, preferably 5 to 25 parts by weight.
- the content of the maleimide compound (C) is 30 to 80 parts by weight, for example, 30 parts by weight, 35 parts by weight, 40 parts by weight, 45 parts by weight, 50 parts by weight parts, 55 parts by weight, 60 parts by weight, 65 parts by weight, 70 parts by weight, 75 parts by weight, or 80 parts by weight, preferably 35 to 70 parts by weight.
- the epoxy resin (A) can be selected from dicyclopentadiene epoxy resin, phosphorus-containing epoxy resin, isocyanate modified epoxy resin, biphenyl epoxy resin, bisphenol A type epoxy resin, phenol type novolac epoxy resin, o-cresol type epoxy resin, epoxidized polybutadiene resin, epoxy resin containing naphthalene ring, bisphenol F type epoxy resin, trifunctional epoxy resin , hydrogenated bisphenol A epoxy resin or hydrogenated bisphenol F type epoxy in any one or a combination of at least two, wherein a typical but non-limiting combination is: dicyclopentadiene epoxy resin and phosphorus-containing epoxy resin Epoxy resin, biphenyl epoxy resin and bisphenol A type epoxy resin, o-cresol type epoxy resin and epoxidized polybutadiene resin, o-cresol type epoxy resin and dicyclopentadiene type epoxy resin resin.
- the phosphorus-containing benzoxazine resin (B) containing an unsaturated bond in the terminal group is a phosphorus-containing benzoxazine resin containing an unsaturated group in the molecular terminal group.
- the phosphorus-containing benzoxazine resin (B) containing an unsaturated bond at the end group has the following structure:
- Q is a substituted or unsubstituted unsaturated bond-containing group
- n is the average number of repeating units , is any number from 0 to 10, such as 0, 0.1, 1, 1.5, 2, 3, 4, 5, 6, 7, 8, 9, 10, etc.;
- R 1 is one of H, C1-C4 (such as C2 or C3) straight-chain or branched-chain alkane, substituted or unsubstituted aryl, and substituted or unsubstituted aryloxy;
- Y is selected from the following structures:
- Z is a covalent bond or is selected from the following structures:
- Q is a group that forms a hydrophobic alkyl chain after curing, more preferably a substituted or unsubstituted C2-C10 alkenyl group, a substituted or unsubstituted styryl group, and a substituted or unsubstituted acrylate group one of substituted or unsubstituted vinyl groups, substituted or unsubstituted allyl groups, substituted or unsubstituted styryl groups, and substituted or unsubstituted phenyl-containing acrylate groups.
- substitution referred to throughout the present invention refers to substitution by halogen, alkyl, alkoxy and other substituents.
- the end group-containing unsaturated phosphorus-containing benzoxazine resin is obtained by reacting a phosphorus-containing diphenol compound, an unsaturated bond-containing amine compound and methanol.
- the phosphorus-containing benzoxazine resin whose terminal group contains an unsaturated bond according to the present invention is selected from one of formula (a) and formula (b) or a combination of at least two:
- Y and Z can be the same or different.
- Y and Z are independently selected from the following structures:
- formula (a) is selected from at least one of the following formulas (a1), (a2) or (a3) or a combination of two or more thereof:
- the Q in the formulae (a1) to (a3) has the same selection range as in the formula (B).
- formula (b) is selected from at least one of the following formulas (b1), (b2), (b3), (b4) or (b5) or a combination of two or more thereof:
- both of the n and Q have the same selection range as in the formula (B).
- the terminal unsaturated bond in the phosphorus-containing benzoxazine resin (B) containing an unsaturated bond in the terminal group of the present invention is selected from vinyl, styryl, allyl or phenyl group. Any one or a combination of at least two of the acrylate groups.
- the phosphorus-containing benzoxazine resin (B) whose terminal group contains an unsaturated bond according to the present invention is exemplified but not limited to the following structure:
- n has the same selection range as in formula (B).
- the maleimide compound (C) is a compound, monomer, mixture, oligomer or polymer containing a maleimide functional group in the molecule.
- the maleimide compound used in the present invention is not particularly limited, and can be any one or more types of prepregs suitable for prepregs, copper-clad foils, resin films, resin-coated copper foils, laminates or Maleimide compounds for printed circuit board fabrication.
- the prepolymer is selected from the group consisting of a diallyl compound and a maleimide compound, a diamine and a maleimide compound, a polyfunctional amine and a maleimide compound. Any one or a combination of at least two of a prepolymer of an imide compound or a prepolymer of an acidic phenol compound and a maleimide compound.
- the maleimide compound may be under the trade names of BMI-70, BMI-80, BMI-1000, BMI-1000H, BMI-1100, BMI-1100H, BMI-2000, BMI-2300, BMI -3000, BMI-3000H, BMI-4000H, BMI-5000, BMI-5100, BMI-7000 and BMI-7000H are maleimide compounds produced by Daiwakasei Corporation.
- the trade names are BMI, BMI-70, BMI-80 and other maleimide compounds produced by Japan KI Chemical.
- the trade names are D936, D937, D939, D950 and other maleimide compounds produced by Sichuan Dongcai Technology Co., Ltd.
- the maleimide compound containing aliphatic long chain structure can be traded under the trade names of BMI-1400, BMI-1500, BMI-1700, BMI-2500, BMI-3000, BMI-5000 and BMI-6000 etc.
- Maleimide compounds produced by Designer Molecular Company can be traded under the trade names of BMI-1400, BMI-1500, BMI-1700, BMI-2500, BMI-3000, BMI-5000 and BMI-6000 etc.
- the resin composition of the present invention may further contain a flame retardant (D).
- the flame retardant (D) is selected from resorcinol-bis(diphenyl phosphate), bisphenol A-bis(diphenyl phosphate), resorcinol-bis(2,6- Any one or a combination of at least two of xylyl phosphate), dimethyl methyl phosphate, additive phosphazene compound or reactive phosphazene compound.
- the content of the flame retardant (D) is 0.1 to 20 parts by weight, such as 0.1 parts by weight, 0.5 parts by weight, 1 part by weight, 2 parts by weight, 5 parts by weight, 8 parts by weight parts by weight, 10 parts by weight, 12 parts by weight or 20 parts by weight.
- the resin composition of the present invention may further contain a filler (E).
- the filler (E) is selected from any one of aluminum hydroxide, silica, stone powder, boehmite, zeolite, wollastonite, magnesium oxide, calcium silicate, calcium carbonate, clay or mica or a combination of at least two.
- the physical form of the filler can be flake, rod, spherical, hollow spherical, angular, granular, fibrous or plate, and can be selectively treated with a silane coupling agent.
- the content of the filler (E) is 10 to 250 parts by weight, for example, 10 parts by weight, 15 parts by weight, 20 parts by weight, 25 parts by weight, 40 parts by weight, 50 parts by weight , 70 parts by weight, 80 parts by weight, 100 parts by weight, 120 parts by weight, 150 parts by weight, 200 parts by weight or 250 parts by weight.
- the resin composition of the present invention may further contain a polyphenylene ether resin (F).
- the polyphenylene ether resin (F) is selected from hydroxyl-terminated polyphenylene ether and/or unsaturated double bond-terminated polyphenylene ether resin, commercially available hydroxyl-terminated polyphenylene ether and/or unsaturated bis
- bond-terminated polyphenylene ether resins include models OPE-2ST and OPE-2EA available from MITSUBISHI GAS CHEMICAL, products SA-90 and SA-9000 available from SABIC , PP807 products that can be purchased from Jinyi Chemical, and polyphenylene ether resins that can be purchased from Asahi Kasei (ASAHI KASEI).
- the content of the polyphenylene ether resin (F) is 0.1 to 30 parts by weight, such as 0.1 parts by weight, 1 part by weight, 5 parts by weight, 10 parts by weight, 15 parts by weight, 20 parts by weight , 25 parts by weight or 30 parts by weight.
- the resin composition of the present invention may further contain an active ester resin (G).
- the active ester resin is not particularly limited, and refers to a resin having an active ester group in its structure. Preferred are active ester compounds containing dicyclopentadiene-type diphenol structure, active ester compounds containing naphthalene structure, active ester compounds containing phenol novolak acetylated compounds, and active ester compounds containing phenol novolac benzoyl compounds Among them, the ester compound is more preferably a naphthalene structure-containing active ester compound or a dicyclopentadiene-type diphenol structure-containing active ester compound.
- Dicyclopentadiene-type diphenol structure means a divalent structural unit formed of phenylene-dicyclopentylene-phenylene.
- active ester compounds containing a dicyclopentadiene diphenol structure include "EXB9451”, “EXB9460”, “EXB9460S”, “HPC-8000”, “HPC-8000H”, “HPC- 8000-65T”, “HPC-8000H-65TM”, “EXB-8000L”, “EXB-8000L-65TM” (manufactured by DIC Corporation), etc.; the active ester compounds containing naphthalene structure include “EXB9416-70BK", “ EXB-8150-65T” (manufactured by DIC Co., Ltd.), etc.; “DC808” (manufactured by Mitsubishi Chemical Co., Ltd.), etc.; Examples of active ester compounds include “YLH1026” (manufactured by Mitsubishi Chemical Co., Ltd.), etc.; “DC808” (manufactured by Mitsubishi Chemical Co., Ltd.) and the like as active ester curing agents
- the number average molecular weight of the active ester resin is below 1800, and the molecular weight can be, for example, 500, 550, 600, 750, 820, 1050, 1200, 1450 or 1800, etc.
- the content of the active ester resin (G) is 0.1 to 30 parts by weight, such as 0.1 parts by weight, 1 part by weight, 5 parts by weight, 10 parts by weight, 15 parts by weight, 20 parts by weight, 25 parts by weight or 30 parts by weight.
- the resin composition of the present invention may further contain a curing accelerator (H).
- the curing accelerator is selected from any one or a combination of at least two of imidazole accelerators and derivatives thereof, pyridines, Lewis acids, amines, phenolic compounds or cyanate ester compounds.
- the content of the curing accelerator (H) is 0.1 to 5 parts by weight, such as 0.1 part by weight, 0.5 part by weight, 1 part by weight, 5 parts by weight or 5 parts by weight.
- the resin composition of the present invention in parts by weight of organic solids, includes the following components:
- the present invention provides a prepreg, resin film or resin-coated copper foil, the prepreg, resin film or resin-coated copper foil comprising the halogen-free flame retardant resin composition described in the first aspect .
- Prepreg is a resin matrix impregnated with continuous fibers or fabrics under strictly controlled conditions to make a composition of resin matrix and reinforcement, which is an intermediate material for the manufacture of composite materials.
- the prepreg of the present invention includes a base material and a halogen-free resin composition attached to the base material.
- the base material is a non-woven fabric or other fabric, and typically but not limitedly includes natural fibers, organic synthetic fibers or inorganic fibers and the like.
- the prepreg is obtained by impregnating and drying the base material in the halogen-free flame retardant resin composition provided in the first aspect;
- the halogen-free flame retardant resin composition adhered to the base material after impregnation and drying.
- the impregnated glass cloth is heated at 140-210°C (for example, 150°C, 160°C, 170°C, 180°C, 190°C, 200°C) °C etc.) in an oven by heating and drying for 1 to 15 minutes (for example, 2 minutes, 4 minutes, 6 minutes, 8 minutes, 10 minutes, 12 minutes, etc.).
- the resin film is formed by semi-curing the resin composition described in the first aspect after baking and heating.
- the resin film can be obtained by coating the resin composition described in the first aspect on the release material, baking, heating, and semi-curing, and then removing the release material.
- the resin-coated copper foil is formed by coating the resin composition described in the first aspect on the copper foil and then semi-curing after baking and heating.
- the present invention provides an insulating board, the insulating board includes at least one piece of the prepreg described in the second aspect.
- the present invention provides a metal foil clad laminate, the metal foil clad laminate comprising at least one of the prepregs described in the second aspect and one or both sides of the laminated prepreg. side foil.
- Laminate is a kind of laminate, which is a whole by lamination and thermocompression of one or more layers of fibers or fabrics (ie prepregs) impregnated with resin.
- the present invention provides a printed circuit board, the printed circuit board comprising at least one prepreg according to the second aspect, or at least one insulating board according to the third aspect, or at least one sheet The metal foil-clad laminate described in the fourth aspect.
- compositions or articles containing a plurality of elements are not limited to only those elements listed herein, but can also include other elements not expressly listed, but which are generally inherent to the composition or article.
- the present invention at least has the following beneficial effects:
- the phosphorus-containing benzoxazine resin whose end groups contain unsaturated bonds provides the unsaturated bonds to react with maleimide, thereby increasing the crosslinking density, and at the same time due to the benzoxazine
- the role of the oxazine ring effectively inhibits the increase in hygroscopicity and the decrease in thermal reliability and dielectric properties caused by phosphorus elements. Dimensional stability is also significantly improved.
- the phosphorus-containing benzoxazine resin component whose end groups contain unsaturated bonds used in the present invention can effectively solve the problem of halogen-free flame retardant due to the phosphorus element contained in its molecular structure.
- the halogen-free flame retardant resin composition provided in the present invention effectively improves the dielectric properties of the resin composition while ensuring that the resin composition has high Tg and high heat resistance; Laminates for printed circuits have excellent performance and excellent dimensional stability.
- the Tg of the laminate prepared by the halogen-free flame retardant resin composition provided by the present invention can reach above 200°C, the dielectric constant can reach below 3.5, the dielectric loss can reach below 0.004, and the thermal delamination time can reach 60min.
- the central value of dimensional stability test is below 500 (preferably below 300).
- the following preparation example exemplarily provides the preparation method of the phosphorus-containing benzoxazine resin whose terminal group contains an unsaturated bond:
- A1 DCPD type epoxy resin with model HP-7200H-75M purchased from DIC in Japan, epoxy equivalent 270;
- A2 Biphenyl epoxy resin with model NC-3000H purchased from Nippon Kayaku, epoxy equivalent 290;
- A3 Trifunctional epoxy resin with model TFE-1250 purchased from Changchun Artificial Resin Factory, epoxy equivalent of 215;
- C2 D950 modified maleimide purchased from Sichuan Dongcai Technology
- D1 Product model SPB-100 purchased from Otsuka Chemical Co., Ltd., Japan;
- E2 Talc powder AG-609 purchased from U.S. Special Mine;
- the preparation method of the printed circuit laminate comprises:
- steps 1 and 2 use 8 pieces of prepreg and 2 pieces of one ounce (35 ⁇ m thick) copper foil to be laminated together;
- the operating conditions of lamination are: the material temperature is 100°C, and the heating rate is controlled to be 2.3°C/min; the material temperature of the outer layer is 90°C, and the full pressure is applied, and the full pressure is 350 psi; during curing, the material is controlled to Temperature at 210 °C, and keep warm for more than 120min.
- the present invention can ensure that the resin composition has high Tg, high heat resistance by adding phosphorus-containing benzoxazine resins containing unsaturated bonds at the end groups to the resin composition formulation.
- the dielectric properties of the resin composition are effectively improved; and the prepreg and printed circuit laminates have excellent properties, as well as excellent dimensional stability, high temperature and high humidity resistance and thermal shock resistance.
- the resin shrinkage value is less than 500ppm, which greatly reduces the difficulty of production control, is beneficial to improve the yield of downstream products and reduce the scrap ratio.
- differential scanning calorimetry it measured according to the TMA method prescribed
- the dielectric constant and dielectric loss factor at 1 GHz were measured according to the method specified in 2.5.5.5 of IPC-TM-650 by the resonance method using the strip line.
- a sheet of 1.00mm thickness is produced.
- a thermal shock cycle refers to: cooling from room temperature to -40°C at a rate of 5°C/min, then heating up to 120°C at a heating rate of 5°C/min, holding for 10 minutes, and then dropping to room temperature at a cooling rate of 5°C/min.
- the present invention illustrates the detailed process equipment and process flow of the present invention through the above-mentioned embodiments, but the present invention is not limited to the above-mentioned detailed process equipment and process flow, that is, it does not mean that the present invention must rely on the above-mentioned detailed process equipment and process flow. Process flow can be implemented. Those skilled in the art should understand that any improvement to the present invention, the equivalent replacement of each raw material of the product of the present invention, the addition of auxiliary components, the selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.
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Abstract
The present invention relates to a halogen-free flame-retardant resin composition and an application thereof. The composition comprises the following components in parts by weight of solid components: (A): 1-40 parts by weight of epoxy resin; (B) 1-30 parts by weight of phosphorus-containing benzoxazine resin having a terminal group containing unsaturated bonds; and (C) 30-80 parts by weight of maleimide compound. The present invention also provides a prepreg, resin film or resin-coated copper foil, insulating board, metal foil-clad laminate, and printed circuit board prepared using the resin composition. According to the halogen-free flame-retardant resin composition in the present invention, dielectric properties of the resin composition is effectively improved while ensuring that the resin composition has high Tg and high heat resistance; and the prepreg and the laminate for use in a printed circuit have excellent performance and high size stability.
Description
本发明涉及层压板技术领域，尤其涉及一种无卤阻燃型树脂组合物及其应用。The invention relates to the technical field of laminates, in particular to a halogen-free flame retardant resin composition and its application.
随着通讯技术的发展，对印制线路基板(CCL)介电常数(D
k)和介电损耗(D
f)的要求越来越高。以手机、笔记本电脑和平板电脑为代表的消费电子领域，在即将到来的5G时代将会作为5G网络的重要应用节点被重新设计和制造。与以往不同的是，其CCL材料需要更低的介电损耗。目前主流的手机以及平板电脑等主板结构均为高密度互连(HDI)设计，对材料固化多次以后的耐热性有更高的要求。在PCB加工过程中，为提高产品的良率，对基板(CCL)和粘结片(Prepreg)的尺寸稳定性都有苛刻要求。开发具有高尺寸稳定性的低介电、高可靠板材有重要的现实意义。
With the development of communication technology, the requirements for the dielectric constant (D k ) and dielectric loss (D f ) of printed circuit substrates (CCL) are getting higher and higher. The field of consumer electronics represented by mobile phones, notebook computers and tablet computers will be redesigned and manufactured as an important application node of 5G networks in the upcoming 5G era. Unlike in the past, its CCL material requires lower dielectric losses. At present, the main board structures of mainstream mobile phones and tablet PCs are all high-density interconnection (HDI) designs, which have higher requirements on the heat resistance of materials after curing for many times. In the process of PCB processing, in order to improve the yield of products, there are strict requirements on the dimensional stability of the substrate (CCL) and the bonding sheet (Prepreg). It is of great practical significance to develop low-dielectric and high-reliability sheets with high dimensional stability.
实现上述目标的难点之一在于，为了实现低介电性能，很多从业人员选择缩合磷酸酯、磷腈及其衍生物等添加型阻燃剂实现无卤阻燃或低卤素阻燃。然而大部分添加型阻燃剂的熔点或软化点较低，会明显降低树脂体系的玻璃化转变温度，加工过程中温度超过一定限度时，特别是超过树脂玻璃化转变温度时导致基板形变急剧增加，尺寸稳定性大大降低。部分从业人员选择含磷结构的环氧树脂和酚醛树脂作为阻燃树脂，但是这部分树脂在耐热性、可靠性以及介电性能方面都不能让人满意。One of the difficulties in achieving the above goals is that in order to achieve low dielectric properties, many practitioners choose additive flame retardants such as condensed phosphate ester, phosphazene and their derivatives to achieve halogen-free flame retardant or low halogen flame retardant. However, the melting point or softening point of most additive flame retardants is low, which will significantly reduce the glass transition temperature of the resin system. When the temperature exceeds a certain limit during processing, especially when the glass transition temperature of the resin exceeds the glass transition temperature of the resin, the deformation of the substrate increases sharply. , the dimensional stability is greatly reduced. Some practitioners choose epoxy resins and phenolic resins containing phosphorus structures as flame retardant resins, but these resins are not satisfactory in terms of heat resistance, reliability and dielectric properties.
另一方面，使用低极性树脂材料易实现低介电性能，但是低极性材料往往刚性不佳，或者粘结力差，在PCB时易产生翘曲和甩线(铜线与基板分离)造 成报废，增加制造成本。On the other hand, the use of low-polarity resin materials is easy to achieve low dielectric properties, but low-polarity materials tend to have poor rigidity or poor adhesion, and are prone to warpage and wire throwing during PCB (copper wire and substrate separation) Scrap and increase manufacturing costs.
因此，如何在保证印制电路用层压板具有高Tg、高耐热性的同时，有效提升其介电性能并使其具有优良的尺寸稳定性，已成为目前亟待解决的技术问题。Therefore, how to effectively improve the dielectric properties and make it have excellent dimensional stability while ensuring that the printed circuit laminate has high Tg and high heat resistance has become an urgent technical problem to be solved.
发明内容SUMMARY OF THE INVENTION
为解决上述技术问题，本发明提供了一种无卤阻燃型树脂组合物及其应用。本发明所提供的无卤阻燃型树脂组合物在保证其具有高Tg、高耐热性的同时，有效提升了树脂组合物的介电性能；并使预浸料和印制电路用层压板具有优异性能的同时具有优良的尺寸稳定性。In order to solve the above technical problems, the present invention provides a halogen-free flame retardant resin composition and its application. The halogen-free flame retardant resin composition provided by the present invention effectively improves the dielectric properties of the resin composition while ensuring that it has high Tg and high heat resistance; It has excellent dimensional stability with excellent performance.
为达此目的，本发明采用以下技术方案：For this purpose, the present invention adopts the following technical solutions:
第一方面，本发明提供了一种无卤阻燃型树脂组合物，以固体组分重量份计，其包括如下组分：In a first aspect, the present invention provides a halogen-free flame retardant resin composition, in parts by weight of solid components, comprising the following components:
(A)环氧树脂：1～40重量份；(A) epoxy resin: 1 to 40 parts by weight;
(B)端基含有不饱和键的含磷苯并噁嗪树脂：1～30重量份；(B) Phosphorus-containing benzoxazine resin whose terminal group contains unsaturated bonds: 1 to 30 parts by weight;
(C)马来酰亚胺化合物：30～80重量份。(C) Maleimide compound: 30 to 80 parts by weight.
发明人在研究过程中发现，通过在树脂组合物中加入端基含有不饱和键的含磷苯并噁嗪树脂组分，(1)噁嗪环在高温时可开环形成羟基，与环氧树脂进行化学交联反应；同时其含有的不饱和键可与马来酰亚胺化合物中的不饱和C＝C双键进行化学交联反应，能使环氧树脂和马来酰亚胺化合物等各组分之间有效交联，解决了环氧树脂和马来酰亚胺化合物之间不能有效反应的难题，由此可以获得较常规苯并噁嗪更好的介电性能。(2)由于其有效交联后形成了稳定可靠的三维交联网络，不仅有效提升了制得的印制电路用层压板的尺寸稳定性，同时，(3)通过化学连接的方式将磷元素引入到苯并噁嗪结构中，可以极大改善磷元素吸湿性强的弊端，在介电性能和耐热性等关键性能之间取得平衡， 实现了在保证印制电路用层压板具有高Tg、高耐热性的同时，有效提升其介电性能并具有优良的尺寸稳定性。During the research process, the inventor found that by adding a phosphorus-containing benzoxazine resin component containing an unsaturated bond at the end group to the resin composition, (1) the oxazine ring can be opened at high temperature to form a hydroxyl group, which is compatible with epoxy resin. The resin undergoes chemical cross-linking reaction; at the same time, the unsaturated bond contained in it can undergo chemical cross-linking reaction with the unsaturated C=C double bond in the maleimide compound, which can make epoxy resin and maleimide compound, etc. The effective crosslinking between the components solves the problem that the epoxy resin and the maleimide compound cannot react effectively, thereby obtaining better dielectric properties than the conventional benzoxazine. (2) Due to its effective cross-linking, a stable and reliable three-dimensional cross-linked network is formed, which not only effectively improves the dimensional stability of the prepared printed circuit laminates, but also (3) chemically links the phosphorus element Introduced into the benzoxazine structure, it can greatly improve the disadvantage of phosphorus element's strong hygroscopicity, achieve a balance between key properties such as dielectric properties and heat resistance, and achieve high Tg in ensuring the laminate for printed circuits. , High heat resistance, at the same time, effectively improve its dielectric properties and have excellent dimensional stability.
本发明中所采用的端基含有不饱和键的含磷苯并噁嗪树脂组分，由于其分子结构中含有磷元素，可有效解决无卤阻燃的问题；另外，由于其分子结构中噁嗪环的存在，最大程度平衡了磷元素易吸水带来的弊端，有效降低板材吸水率的问题，从而提升树脂组合物的介电稳定性和可靠性。相对于添加型阻燃剂，端基含有不饱和键的含磷苯并噁嗪树脂有效保证了磷元素与主体树脂处于化学交联状态，避免磷元素处于游离易析出的状态。即使在超过大部分添加型阻燃剂熔点的温度下仍能保持良好的性能，在温度循环测试，耐湿热测试中表现更稳定。因此，在本发明的树脂组合物中，由于端基含有不饱和键的含磷苯并噁嗪树脂组分的添加，含磷基团与苯并噁嗪结构之间相互配合，同时解决了非反应型阻燃剂容易带来的吸水率上升、尺寸稳定性下降和耐热性下降的问题。The phosphorus-containing benzoxazine resin component whose terminal group contains unsaturated bonds adopted in the present invention can effectively solve the problem of halogen-free flame retardant because of the phosphorus element in its molecular structure; The existence of the oxazine ring balances the drawbacks caused by the easy water absorption of phosphorus elements to the greatest extent, and effectively reduces the problem of water absorption of the board, thereby improving the dielectric stability and reliability of the resin composition. Compared with additive flame retardants, phosphorus-containing benzoxazine resins whose end groups contain unsaturated bonds can effectively ensure that phosphorus elements and the host resin are in a chemically cross-linked state, and prevent phosphorus elements from being free and easy to precipitate. It can maintain good performance even at temperatures exceeding the melting point of most additive flame retardants, and it is more stable in temperature cycling tests and damp heat resistance tests. Therefore, in the resin composition of the present invention, due to the addition of the phosphorus-containing benzoxazine resin component containing an unsaturated bond at the end group, the phosphorus-containing group and the benzoxazine structure cooperate with each other, and at the same time solve the problem of Reactive flame retardants are prone to problems of increased water absorption, decreased dimensional stability, and decreased heat resistance.
本发明中所采用的端基含有不饱和键的含磷苯并噁嗪树脂组分，相对于已有的苯并噁嗪树脂，由于其分子结构中含有不饱和键，可提供更多的交联点与马来酰亚胺化合物反应，更易形成致密的交联网络，并有效降低了介电常数和介电损耗因子。Compared with the existing benzoxazine resin, the phosphorus-containing benzoxazine resin component with unsaturated bond at the end group adopted in the present invention can provide more cross-linking due to the unsaturated bond in its molecular structure. When the junction point reacts with the maleimide compound, it is easier to form a dense cross-linked network, and the dielectric constant and dielectric loss factor are effectively reduced.
本发明的树脂组合物中，所述的环氧树脂(A)的含量为1～40重量份，例如可以是1重量份、2重量份、5重量份、10重量份、15重量份、20重量份、25重量份、30重量份、35重量份或40重量份，优选为5～30重量份。In the resin composition of the present invention, the content of the epoxy resin (A) is 1 to 40 parts by weight, for example, 1 part by weight, 2 parts by weight, 5 parts by weight, 10 parts by weight, 15 parts by weight, 20 parts by weight parts by weight, 25 parts by weight, 30 parts by weight, 35 parts by weight or 40 parts by weight, preferably 5 to 30 parts by weight.
本发明的树脂组合物中，所述的端基含有不饱和键的含磷苯并噁嗪树脂(B)的含量为1～30重量份，例如可以是1重量份、2重量份、5重量份、10重量份、15重量份、20重量份、25重量份或30重量份，优选为5～25重量份。In the resin composition of the present invention, the content of the phosphorus-containing benzoxazine resin (B) whose terminal groups contain unsaturated bonds is 1 to 30 parts by weight, for example, 1 part by weight, 2 parts by weight, 5 parts by weight part, 10 parts by weight, 15 parts by weight, 20 parts by weight, 25 parts by weight or 30 parts by weight, preferably 5 to 25 parts by weight.
本发明的树脂组合物中，所述的马来酰亚胺化合物(C)的含量为30～80重 量份，例如可以是30重量份、35重量份、40重量份、45重量份、50重量份、55重量份、60重量份、65重量份、70重量份、75重量份或80重量份，优选为35～70重量份。In the resin composition of the present invention, the content of the maleimide compound (C) is 30 to 80 parts by weight, for example, 30 parts by weight, 35 parts by weight, 40 parts by weight, 45 parts by weight, 50 parts by weight parts, 55 parts by weight, 60 parts by weight, 65 parts by weight, 70 parts by weight, 75 parts by weight, or 80 parts by weight, preferably 35 to 70 parts by weight.
本发明的树脂组合物中，所述的环氧树脂(A)可以选自双环戊二烯环氧树脂、含磷环氧树脂、异氰酸酯改性环氧树脂、联苯环氧树脂、双酚A型环氧树脂、苯酚型酚醛环氧树脂、邻甲酚醛型环氧树脂、环氧化聚丁二烯树脂、含萘环的环氧树脂、双酚F型环氧树脂，三官能环氧树脂、氢化的双酚A环氧树脂或氢化的双酚F型环氧中的任意一种或至少两种的组合，其中典型但非限制性的组合为：双环戊二烯环氧树脂和含磷环氧树脂、联苯环氧树脂和双酚A型环氧树脂、邻甲酚醛型环氧树脂和环氧化聚丁二烯树脂，邻甲酚醛型环氧树脂和双环戊二烯型环氧树脂。In the resin composition of the present invention, the epoxy resin (A) can be selected from dicyclopentadiene epoxy resin, phosphorus-containing epoxy resin, isocyanate modified epoxy resin, biphenyl epoxy resin, bisphenol A type epoxy resin, phenol type novolac epoxy resin, o-cresol type epoxy resin, epoxidized polybutadiene resin, epoxy resin containing naphthalene ring, bisphenol F type epoxy resin, trifunctional epoxy resin , hydrogenated bisphenol A epoxy resin or hydrogenated bisphenol F type epoxy in any one or a combination of at least two, wherein a typical but non-limiting combination is: dicyclopentadiene epoxy resin and phosphorus-containing epoxy resin Epoxy resin, biphenyl epoxy resin and bisphenol A type epoxy resin, o-cresol type epoxy resin and epoxidized polybutadiene resin, o-cresol type epoxy resin and dicyclopentadiene type epoxy resin resin.
本发明的树脂组合物中，所述的端基含有不饱和键的含磷苯并噁嗪树脂(B)为分子端基含有不饱和基团的含磷苯并噁嗪树脂。In the resin composition of the present invention, the phosphorus-containing benzoxazine resin (B) containing an unsaturated bond in the terminal group is a phosphorus-containing benzoxazine resin containing an unsaturated group in the molecular terminal group.
优选地，所述的端基含有不饱和键的含磷苯并噁嗪树脂(B)，其结构如下式：Preferably, the phosphorus-containing benzoxazine resin (B) containing an unsaturated bond at the end group has the following structure:
Q为取代或未取代的含不饱和键的基团；Q is a substituted or unsubstituted unsaturated bond-containing group;
X为
X is
其中m为重复单元数量的平均值，为3～10的任意数，例如3，3.5，4，4.5，5，5.5，6，7，8，9，10等；n为重复单元数量的平均值，为0～10的任意数，例如0，0.1，1，1.5，2，3，4，5，6，7，8，9，10等；Where m is the average number of repeating units, which is any number from 3 to 10, such as 3, 3.5, 4, 4.5, 5, 5.5, 6, 7, 8, 9, 10, etc.; n is the average number of repeating units , is any number from 0 to 10, such as 0, 0.1, 1, 1.5, 2, 3, 4, 5, 6, 7, 8, 9, 10, etc.;
R
1为H、C1～C4(例如C2或C3)的直链或支链烷烃、取代或未取代的芳基、取代或未取代的芳氧基中的一种；
R 1 is one of H, C1-C4 (such as C2 or C3) straight-chain or branched-chain alkane, substituted or unsubstituted aryl, and substituted or unsubstituted aryloxy;
Y选自下列结构：Y is selected from the following structures:
其中，
中穿过苯环的两条直线代表链接键，在羟基邻位的为甲基；
in, The two straight lines passing through the benzene ring represent the linkage bond, and the one in the ortho-position of the hydroxyl group is a methyl group;
Z为共价键或选自下列结构：Z is a covalent bond or is selected from the following structures:
优选地，Q为固化后形成疏水性烷基链的基团，进一步优选为取代或未取代的C2-C10烯基、取代或未取代的苯乙烯基、取代或未取代的丙烯酸酯基团中的一种，更优选为取代或未取代的乙烯基、取代或未取代的烯丙基、取代或未取代的苯乙烯基、取代或未取代的含有苯基的丙烯酸酯基中的一种。Preferably, Q is a group that forms a hydrophobic alkyl chain after curing, more preferably a substituted or unsubstituted C2-C10 alkenyl group, a substituted or unsubstituted styryl group, and a substituted or unsubstituted acrylate group one of substituted or unsubstituted vinyl groups, substituted or unsubstituted allyl groups, substituted or unsubstituted styryl groups, and substituted or unsubstituted phenyl-containing acrylate groups.
本发明全文所指的取代是指被卤素、烷基、烷氧基等取代基取代。The substitution referred to throughout the present invention refers to substitution by halogen, alkyl, alkoxy and other substituents.
优选地，所述端基含有不饱和含磷苯并噁嗪树脂由含磷元素的二酚化合物、含不饱和键的胺类化合物和甲醇通过反应而得。Preferably, the end group-containing unsaturated phosphorus-containing benzoxazine resin is obtained by reacting a phosphorus-containing diphenol compound, an unsaturated bond-containing amine compound and methanol.
本发明所述的端基含有不饱和键的含磷苯并噁嗪树脂选自式(a)、式(b)中的一种或至少两种的组合：The phosphorus-containing benzoxazine resin whose terminal group contains an unsaturated bond according to the present invention is selected from one of formula (a) and formula (b) or a combination of at least two:
式(a)Formula (a)
式(b)Formula (b)
式(a)、式(b)中，所述m、n、R
1、Q、Z和Y均具有与式(B)中相同的选择范围。
In formula (a) and formula (b), the m, n, R 1 , Q, Z and Y all have the same selection range as in formula (B).
优选地，Y和Z可相同也可不同。Y和Z独立选自下列结构：Preferably, Y and Z can be the same or different. Y and Z are independently selected from the following structures:
优选地，式(a)选自如下式(a1)、(a2)或(a3)中的至少一种或两种及其以上的组合：Preferably, formula (a) is selected from at least one of the following formulas (a1), (a2) or (a3) or a combination of two or more thereof:
式(a1)至(a3)中所述Q具有与式(B)中相同的选择范围。The Q in the formulae (a1) to (a3) has the same selection range as in the formula (B).
优选地，式(b)选自如下式(b1)、(b2)、(b3)、(b4)或(b5)中的至少一种或两种及其以上的组合：Preferably, formula (b) is selected from at least one of the following formulas (b1), (b2), (b3), (b4) or (b5) or a combination of two or more thereof:
式(b1)至(b5)中，所述n和Q均具有与式(B)中相同的选择范围。In the formulae (b1) to (b5), both of the n and Q have the same selection range as in the formula (B).
进一步优选地，本发明所述的端基含有不饱和键的含磷苯并噁嗪树脂(B)中的端基不饱和键选自乙烯基、苯乙烯基、烯丙基或含有苯基的丙烯酸酯基中的任意一种或至少两种组合。Further preferably, the terminal unsaturated bond in the phosphorus-containing benzoxazine resin (B) containing an unsaturated bond in the terminal group of the present invention is selected from vinyl, styryl, allyl or phenyl group. Any one or a combination of at least two of the acrylate groups.
进一步优选地，本发明所述的端基含有不饱和键的含磷苯并噁嗪树脂(B)举例但不限于如下结构：Further preferably, the phosphorus-containing benzoxazine resin (B) whose terminal group contains an unsaturated bond according to the present invention is exemplified but not limited to the following structure:
其中，所述n具有与式(B)中相同的选择范围。Wherein, the n has the same selection range as in formula (B).
本发明的树脂组合物中，所述的马来酰亚胺化合物(C)为分子中含有马来酰亚胺官能团的化合物、单体、混合物、低聚物或聚合物。若未特别指明，本发明采用的马来酰亚胺化合物并不特别限制，且可为任一种或多种适用于半固化片、覆铜箔的半固化片、树脂膜、涂树脂铜箔、层压板或印刷电路板制作的马来酰亚胺化合物。具体实例包括但不限于：4,4'-二苯甲烷双马来酰亚胺、聚苯甲烷马来酰亚胺、间-伸苯基双马来酰亚胺、双酚A二苯基醚双马来酰亚胺、3,3'-二甲基-5,5'-二乙基-4,4'-二苯基甲烷双马来酰亚胺、4-甲基-1,3-伸苯基双马来酰亚胺、1,6-双马来酰亚胺-(2,2,4-三甲基)己烷、2,3-二甲基苯马来酰亚胺、2,6-二甲基苯马来酰亚胺、N-苯基马来酰亚胺、含脂肪族长链结构的马来酰亚胺类化合物及其预聚物中的任意一种或至少两种的组合，其中典型但非限制性的组合为：4,4'-二苯甲烷双马来酰亚胺和聚苯甲烷马来酰亚胺、间-伸苯基双马来酰亚胺和双酚A二苯基醚双马来酰亚胺、1,6-双马来酰亚胺-(2,2,4-三甲基)己烷和2,3-二甲基苯马来酰亚胺等。In the resin composition of the present invention, the maleimide compound (C) is a compound, monomer, mixture, oligomer or polymer containing a maleimide functional group in the molecule. Unless otherwise specified, the maleimide compound used in the present invention is not particularly limited, and can be any one or more types of prepregs suitable for prepregs, copper-clad foils, resin films, resin-coated copper foils, laminates or Maleimide compounds for printed circuit board fabrication. Specific examples include, but are not limited to: 4,4'-diphenylmethanebismaleimide, polyphenylenemethanemaleimide, m-phenylene bismaleimide, bisphenol A diphenyl ether Bismaleimide, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethanebismaleimide, 4-methyl-1,3- phenylene bismaleimide, 1,6-bismaleimide-(2,2,4-trimethyl)hexane, 2,3-dimethylbenzenemaleimide, 2 , any one or at least two of 6-dimethylbenzenemaleimide, N-phenylmaleimide, maleimide compounds containing aliphatic long-chain structure and prepolymers thereof , wherein typical but non-limiting combinations are: 4,4'-diphenylmethanebismaleimide and polyphenylenemethanemaleimide, m-phenylene bismaleimide and bis-maleimide Phenol A diphenyl ether bismaleimide, 1,6-bismaleimide-(2,2,4-trimethyl)hexane and 2,3-dimethylbenzenemaleimide Amines etc.
优选地，所述的预聚物选自二烯丙基化合物与马来酰亚胺类化合物的预聚物、二胺与马来酰亚胺类化合物的预聚物、多官能胺与马来酰亚胺类化合物的预聚物或酸性酚化合物与马来酰亚胺类化合物的预聚物中的任意一种或至少两种的组合。Preferably, the prepolymer is selected from the group consisting of a diallyl compound and a maleimide compound, a diamine and a maleimide compound, a polyfunctional amine and a maleimide compound. Any one or a combination of at least two of a prepolymer of an imide compound or a prepolymer of an acidic phenol compound and a maleimide compound.
举例而言，所述马来酰亚胺化合物可为商品名为BMI-70、BMI-80、BMI-1000、BMI-1000H、BMI-1100、BMI-1100H、BMI-2000、BMI-2300、 BMI-3000、BMI-3000H、BMI-4000H、BMI-5000、BMI-5100、BMI-7000及BMI-7000H等由Daiwakasei公司生产的马来酰亚胺化合物。商品名为BMI、BMI-70、BMI-80等由日本KI Chemical生产的马来酰亚胺化合物。商品名为D936、D937、D939、D950等由四川东材科技股份有限公司生产的马来酰亚胺化合物。For example, the maleimide compound may be under the trade names of BMI-70, BMI-80, BMI-1000, BMI-1000H, BMI-1100, BMI-1100H, BMI-2000, BMI-2300, BMI -3000, BMI-3000H, BMI-4000H, BMI-5000, BMI-5100, BMI-7000 and BMI-7000H are maleimide compounds produced by Daiwakasei Corporation. The trade names are BMI, BMI-70, BMI-80 and other maleimide compounds produced by Japan KI Chemical. The trade names are D936, D937, D939, D950 and other maleimide compounds produced by Sichuan Dongcai Technology Co., Ltd.
举例而言，所述含脂肪族长链结构的马来酰亚胺化合物可为商品名为BMI-1400、BMI-1500、BMI-1700、BMI-2500、BMI-3000、BMI-5000及BMI-6000等由设计者分子公司生产的马来酰亚胺化合物。For example, the maleimide compound containing aliphatic long chain structure can be traded under the trade names of BMI-1400, BMI-1500, BMI-1700, BMI-2500, BMI-3000, BMI-5000 and BMI-6000 etc. Maleimide compounds produced by Designer Molecular Company.
本发明的树脂组合物中，还可以进一步包含阻燃剂(D)。The resin composition of the present invention may further contain a flame retardant (D).
优选地，所述的阻燃剂(D)选自间苯二酚-双(磷酸二苯酯)、双酚A-双(磷酸二苯酯)、间苯二酚-双(2,6-二甲苯基磷酸酯)、甲基磷酸二甲酯、添加型磷腈化合物或反应型磷腈化合物中的任意一种或至少两种的组合。Preferably, the flame retardant (D) is selected from resorcinol-bis(diphenyl phosphate), bisphenol A-bis(diphenyl phosphate), resorcinol-bis(2,6- Any one or a combination of at least two of xylyl phosphate), dimethyl methyl phosphate, additive phosphazene compound or reactive phosphazene compound.
优选地，所述的树脂组合物中，阻燃剂(D)的含量为0.1～20重量份，例如可以是0.1重量份、0.5重量份、1重量份、2重量份、5重量份、8重量份、10重量份、12重量份或20重量份。Preferably, in the resin composition, the content of the flame retardant (D) is 0.1 to 20 parts by weight, such as 0.1 parts by weight, 0.5 parts by weight, 1 part by weight, 2 parts by weight, 5 parts by weight, 8 parts by weight parts by weight, 10 parts by weight, 12 parts by weight or 20 parts by weight.
本发明的树脂组合物中，还可以进一步包含填料(E)。The resin composition of the present invention may further contain a filler (E).
优选地，所述的填料(E)选自氢氧化铝、二氧化硅、石粉、勃姆石、沸石、硅灰石、氧化镁、硅酸钙、碳酸钙、粘土或云母中的任意一种或至少两种的组合。Preferably, the filler (E) is selected from any one of aluminum hydroxide, silica, stone powder, boehmite, zeolite, wollastonite, magnesium oxide, calcium silicate, calcium carbonate, clay or mica or a combination of at least two.
本发明中，所述填料的物理形态可为片状、棒状、球形、空心球形、角形、粒状、纤维状或板状等，可选择性以硅烷偶联剂处理。In the present invention, the physical form of the filler can be flake, rod, spherical, hollow spherical, angular, granular, fibrous or plate, and can be selectively treated with a silane coupling agent.
优选地，所述的树脂组合物中，填料(E)的含量为10～250重量份，例如可以是10重量份、15重量份、20重量份、25重量份、40重量份、50重量份、 70重量份、80重量份、100重量份、120重量份、150重量份、200重量份或250重量份。Preferably, in the resin composition, the content of the filler (E) is 10 to 250 parts by weight, for example, 10 parts by weight, 15 parts by weight, 20 parts by weight, 25 parts by weight, 40 parts by weight, 50 parts by weight , 70 parts by weight, 80 parts by weight, 100 parts by weight, 120 parts by weight, 150 parts by weight, 200 parts by weight or 250 parts by weight.
本发明的树脂组合物中，还可以进一步包含聚苯醚树脂(F)。The resin composition of the present invention may further contain a polyphenylene ether resin (F).
所述的聚苯醚树脂(F)选自羟基封端的聚苯醚和/或不饱和双键封端的聚苯醚树脂，商业上可购得的羟基封端的聚苯醚和/或不饱和双键封端的聚苯醚树脂的实例包括可购自三菱瓦斯化学(MITSUBISHI GAS CHEMICAL)的型号为OPE-2ST及OPE-2EA的产品，可购自SABIC的型号为SA-90及SA-9000的产品，可购自晋一化工的型号为PP807的产品，以及可购自旭化成(ASAHI KASEI)的聚苯醚树脂等等。The polyphenylene ether resin (F) is selected from hydroxyl-terminated polyphenylene ether and/or unsaturated double bond-terminated polyphenylene ether resin, commercially available hydroxyl-terminated polyphenylene ether and/or unsaturated bis Examples of bond-terminated polyphenylene ether resins include models OPE-2ST and OPE-2EA available from MITSUBISHI GAS CHEMICAL, products SA-90 and SA-9000 available from SABIC , PP807 products that can be purchased from Jinyi Chemical, and polyphenylene ether resins that can be purchased from Asahi Kasei (ASAHI KASEI).
所述的树脂组合物中，聚苯醚树脂(F)的含量为0.1～30重量份，例如可以是0.1重量份、1重量份、5重量份、10重量份、15重量份、20重量份、25重量份或30重量份。In the resin composition, the content of the polyphenylene ether resin (F) is 0.1 to 30 parts by weight, such as 0.1 parts by weight, 1 part by weight, 5 parts by weight, 10 parts by weight, 15 parts by weight, 20 parts by weight , 25 parts by weight or 30 parts by weight.
本发明的树脂组合物中，还可以进一步包含活性酯树脂(G)。活性酯树脂没有特别限定，是指结构中含有活性的酯基的树脂。优选的是含二环戊二烯型二苯酚结构的活性酯化合物、含萘结构的活性酯化合物、含苯酚酚醛清漆的乙酰基化物的活性酯化合物、含苯酚酚醛清漆的苯甲酰基化物的活性酯化合物，其中，更好是含萘结构的活性酯化合物、含二环戊二烯型二苯酚结构的活性酯化合物。“二环戊二烯型二苯酚结构”表示由亚苯基-二亚环戊基-亚苯基形成的二价结构单元。The resin composition of the present invention may further contain an active ester resin (G). The active ester resin is not particularly limited, and refers to a resin having an active ester group in its structure. Preferred are active ester compounds containing dicyclopentadiene-type diphenol structure, active ester compounds containing naphthalene structure, active ester compounds containing phenol novolak acetylated compounds, and active ester compounds containing phenol novolac benzoyl compounds Among them, the ester compound is more preferably a naphthalene structure-containing active ester compound or a dicyclopentadiene-type diphenol structure-containing active ester compound. "Dicyclopentadiene-type diphenol structure" means a divalent structural unit formed of phenylene-dicyclopentylene-phenylene.
活性酯树脂市售品，含二环戊二烯型二苯酚结构的活性酯化合物可列举“EXB9451”、“EXB9460”、“EXB9460S”、“HPC-8000”、“HPC-8000H”、“HPC-8000-65T”、“HPC-8000H-65TM”、“EXB-8000L”、“EXB-8000L-65TM”(DIC株式会社制)等；含萘结构的活性酯化合物可列举“EXB9416-70BK”、 “EXB-8150-65T”(DIC株式会社制)等；含苯酚酚醛清漆的乙酰基化物的活性酯化合物可列举“DC808”(三菱化学株式会社制)等；含苯酚酚醛清漆的苯甲酰基化物的活性酯化合物可列举“YLH1026”(三菱化学株式会社制)等；作为苯酚酚醛清漆的乙酰基化物的活性酯系固化剂可列举“DC808”(三菱化学株式会社制)等；作为苯酚酚醛清漆的苯甲酰基化物的活性酯系固化剂可列举“YLH1026”(三菱化学株式会社制)、“YLH1030”(三菱化学株式会社制)、“YLH1048”(三菱化学株式会社制)等。Commercially available active ester resins, active ester compounds containing a dicyclopentadiene diphenol structure include "EXB9451", "EXB9460", "EXB9460S", "HPC-8000", "HPC-8000H", "HPC- 8000-65T", "HPC-8000H-65TM", "EXB-8000L", "EXB-8000L-65TM" (manufactured by DIC Corporation), etc.; the active ester compounds containing naphthalene structure include "EXB9416-70BK", " EXB-8150-65T" (manufactured by DIC Co., Ltd.), etc.; "DC808" (manufactured by Mitsubishi Chemical Co., Ltd.), etc.; Examples of active ester compounds include "YLH1026" (manufactured by Mitsubishi Chemical Co., Ltd.), etc.; "DC808" (manufactured by Mitsubishi Chemical Co., Ltd.) and the like as active ester curing agents of acetylated compounds of phenol novolaks; "YLH1026" (made by Mitsubishi Chemical Co., Ltd.), "YLH1030" (made by Mitsubishi Chemical Co., Ltd.), "YLH1048" (made by Mitsubishi Chemical Co., Ltd.), etc. are mentioned as the active ester type hardening|curing agent of a benzoyl compound.
优选地，所述的活性酯树脂的数均分子量为1800以下，分子量例如可以是500、550、600、750、820、1050、1200、1450或1800等。Preferably, the number average molecular weight of the active ester resin is below 1800, and the molecular weight can be, for example, 500, 550, 600, 750, 820, 1050, 1200, 1450 or 1800, etc.
所述的树脂组合物中，活性酯树脂(G)的含量为0.1～30重量份，例如可以是0.1重量份、1重量份、5重量份、10重量份、15重量份、20重量份、25重量份或30重量份。In the resin composition, the content of the active ester resin (G) is 0.1 to 30 parts by weight, such as 0.1 parts by weight, 1 part by weight, 5 parts by weight, 10 parts by weight, 15 parts by weight, 20 parts by weight, 25 parts by weight or 30 parts by weight.
本发明的树脂组合物中，还可以进一步包含固化促进剂(H)。The resin composition of the present invention may further contain a curing accelerator (H).
所述的固化促进剂选自咪唑类促进剂及其衍生物、吡啶类、路易斯酸类、胺类、酚醛类或氰酸酯类化合物中的任意一种或至少两种的组合。The curing accelerator is selected from any one or a combination of at least two of imidazole accelerators and derivatives thereof, pyridines, Lewis acids, amines, phenolic compounds or cyanate ester compounds.
所述的树脂组合物中，固化促进剂(H)的含量为0.1～5重量份，例如可以是0.1重量份、0.5重量份、1重量份、5重量份或5重量份。In the resin composition, the content of the curing accelerator (H) is 0.1 to 5 parts by weight, such as 0.1 part by weight, 0.5 part by weight, 1 part by weight, 5 parts by weight or 5 parts by weight.
作为可选的技术方案，本发明的树脂组合物中，以有机固形物重量份计，包括如下组分：As an optional technical solution, the resin composition of the present invention, in parts by weight of organic solids, includes the following components:
(A)环氧树脂：1～40重量份；(A) epoxy resin: 1 to 40 parts by weight;
(B)端基含有不饱和键的含磷苯并噁嗪树脂：1～30重量份；(B) Phosphorus-containing benzoxazine resin whose terminal group contains unsaturated bonds: 1 to 30 parts by weight;
(C)马来酰亚胺化合物：30～80重量份；(C) maleimide compound: 30 to 80 parts by weight;
(D)阻燃剂：0.1～15重量份；(D) flame retardant: 0.1 to 15 parts by weight;
(E)填料：10～250重量份；(E) Filler: 10-250 parts by weight;
(F)羟基封端的聚苯醚树脂或/和不饱和双键封端的聚苯醚树脂：0.1～30重量份；(F) hydroxyl-terminated polyphenylene ether resin or/and unsaturated double bond-terminated polyphenylene ether resin: 0.1 to 30 parts by weight;
(G)活性酯树脂：0.1～30重量份；(G) Active ester resin: 0.1 to 30 parts by weight;
(H)促进剂：0.1～5重量份。(H) Accelerator: 0.1 to 5 parts by weight.
第二方面，本发明提供了一种预浸料、树脂膜或涂树脂铜箔，所述预浸料、树脂膜或涂树脂铜箔包括第一方面所述的无卤阻燃型树脂组合物。In a second aspect, the present invention provides a prepreg, resin film or resin-coated copper foil, the prepreg, resin film or resin-coated copper foil comprising the halogen-free flame retardant resin composition described in the first aspect .
预浸料是用树脂基体在严格控制的条件下浸渍连续纤维或织物，制成树脂基体与增强体的组合物，是制造复合材料的中间材料。Prepreg is a resin matrix impregnated with continuous fibers or fabrics under strictly controlled conditions to make a composition of resin matrix and reinforcement, which is an intermediate material for the manufacture of composite materials.
本发明所述的预浸料包括基料和附着在所述基料上的无卤树脂组合物。所述基料为无纺织物或其它织物，典型但非限制性的包括天然纤维、有机合成纤维或无机纤维等。The prepreg of the present invention includes a base material and a halogen-free resin composition attached to the base material. The base material is a non-woven fabric or other fabric, and typically but not limitedly includes natural fibers, organic synthetic fibers or inorganic fibers and the like.
优选地，所述预浸料是将所述基料经过在第一方面提供的无卤阻燃型树脂组合物中进行含浸、干燥处理后获得的；即，所述预浸料包括基料及通过含浸、干燥处理后附着在所述基料上的无卤阻燃型树脂组合物。Preferably, the prepreg is obtained by impregnating and drying the base material in the halogen-free flame retardant resin composition provided in the first aspect; The halogen-free flame retardant resin composition adhered to the base material after impregnation and drying.
本发明所述的预浸料的制备方法，本领域技术人员可以参考现有的预浸料的制备方法，本发明不做具体限定，典型但非限制性的所述预浸料的制备方法包括如下步骤：For the preparation method of the prepreg of the present invention, those skilled in the art can refer to the existing preparation method of the prepreg, which is not specifically limited in the present invention, and the typical but non-limiting preparation method of the prepreg includes: Follow the steps below:
使用第一方面提供的无卤阻燃型树脂组合物的胶液含浸基料，将含浸好的玻璃布在140～210℃(例如150℃、160℃、170℃、180℃、190℃、200℃等)的烘箱中加热干燥1～15分钟(例如2分钟、4分钟、6分钟、8分钟、10分钟、12分钟等)制成。Using the glue liquid impregnation base material of the halogen-free flame retardant resin composition provided in the first aspect, the impregnated glass cloth is heated at 140-210°C (for example, 150°C, 160°C, 170°C, 180°C, 190°C, 200°C) ℃ etc.) in an oven by heating and drying for 1 to 15 minutes (for example, 2 minutes, 4 minutes, 6 minutes, 8 minutes, 10 minutes, 12 minutes, etc.).
树脂膜是由第一方面所述的树脂组合物经烘烤加热后半固化而成。具体地， 树脂膜可以由第一方面所述的树脂组合物涂在离型材料上经烘烤加热半固化后除去离型材料获得。The resin film is formed by semi-curing the resin composition described in the first aspect after baking and heating. Specifically, the resin film can be obtained by coating the resin composition described in the first aspect on the release material, baking, heating, and semi-curing, and then removing the release material.
涂树脂铜箔是由第一方面所述的树脂组合物涂在铜箔上经烘烤加热后半固化而成。The resin-coated copper foil is formed by coating the resin composition described in the first aspect on the copper foil and then semi-curing after baking and heating.
第三方面，本发明提供了一种绝缘板，所述绝缘板包括至少一张第二方面所述的预浸料。In a third aspect, the present invention provides an insulating board, the insulating board includes at least one piece of the prepreg described in the second aspect.
第四方面，本发明提供了一种覆金属箔层压板，所述覆金属箔层压板包括至少一张第二方面所述的预浸料以及覆于叠合后的预浸料一侧或两侧的金属箔。In a fourth aspect, the present invention provides a metal foil clad laminate, the metal foil clad laminate comprising at least one of the prepregs described in the second aspect and one or both sides of the laminated prepreg. side foil.
层压板是层压制品的一种，是由一层或多层浸有树脂的纤维或织物(即预浸料)，经叠合、热压结合成的整体。Laminate is a kind of laminate, which is a whole by lamination and thermocompression of one or more layers of fibers or fabrics (ie prepregs) impregnated with resin.
第五方面，本发明提供了一种印刷电路板，所述印刷电路板包括至少一张第二方面所述的预浸料，或至少一张第三方面所述的绝缘板，或至少一张第四方面所述的覆金属箔层压板。In a fifth aspect, the present invention provides a printed circuit board, the printed circuit board comprising at least one prepreg according to the second aspect, or at least one insulating board according to the third aspect, or at least one sheet The metal foil-clad laminate described in the fourth aspect.
在本发明中，用语“包含”、“包括”、“具有”、“含有”或其他任何类似用语均属于开放性连接词，其意欲涵盖非排他性的包括物。举例而言，含有复数要素的组合物或制品并不仅限于本文所列出的此等要素而已，而是还可包括未明确列出但却是该组合物或制品通常固有的其他要素。In the present invention, the terms "comprising", "including", "having", "containing" or any other similar terms are all open linkers intended to encompass non-exclusive inclusions. For example, a composition or article containing a plurality of elements is not limited to only those elements listed herein, but can also include other elements not expressly listed, but which are generally inherent to the composition or article.
与现有技术相比，本发明至少具有以下有益效果：Compared with the prior art, the present invention at least has the following beneficial effects:
(1)本发明通过在树脂组合物中加入端基含有不饱和键的含磷苯并噁嗪树脂组分，其能使环氧树脂和马来酰亚胺化合物等各组分之间有效交联，解决了环氧树脂和马来酰亚胺化合物之间不能有效反应的问题，同时，由于其有效交联后形成了稳定可靠的三维交联网络，不仅有效提升了制得的印制电路用层压 板的尺寸稳定性，同时，还在介电性能和耐热性等关键性能之间取得平衡，实现了在保证印制电路用层压板具有高Tg、高耐热性的同时，有效提升其介电性能并具有优良的尺寸稳定性。(1) In the present invention, by adding a phosphorus-containing benzoxazine resin component containing an unsaturated bond in the terminal group to the resin composition, it can effectively cross-link between components such as epoxy resin and maleimide compound. It solves the problem of ineffective reaction between epoxy resin and maleimide compound. At the same time, because it forms a stable and reliable three-dimensional cross-linked network after effective cross-linking, it not only effectively improves the printed circuit. The dimensional stability of the laminates, and at the same time, a balance between key properties such as dielectric properties and heat resistance is achieved, which effectively improves the laminates for printed circuits while ensuring high Tg and high heat resistance. Its dielectric properties and has excellent dimensional stability.
(2)在本发明的树脂组合物中，端基含有不饱和键的含磷苯并噁嗪树脂提供了不饱和键与马来酰亚胺进行反应，增加了交联密度，同时由于苯并噁嗪环的作用，有效抑制了磷元素带来的吸湿性增加，热可靠性和介电性能下降的问题。尺寸稳定性也有明显的提升。(2) In the resin composition of the present invention, the phosphorus-containing benzoxazine resin whose end groups contain unsaturated bonds provides the unsaturated bonds to react with maleimide, thereby increasing the crosslinking density, and at the same time due to the benzoxazine The role of the oxazine ring effectively inhibits the increase in hygroscopicity and the decrease in thermal reliability and dielectric properties caused by phosphorus elements. Dimensional stability is also significantly improved.
(3)本发明中所采用的端基含有不饱和键的含磷苯并噁嗪树脂组分，由于其分子结构中含有磷元素，可有效解决无卤阻燃的问题。(3) The phosphorus-containing benzoxazine resin component whose end groups contain unsaturated bonds used in the present invention can effectively solve the problem of halogen-free flame retardant due to the phosphorus element contained in its molecular structure.
(4)本发明中所提供的无卤阻燃型树脂组合物在保证树脂组合物具有高Tg、高耐热性的同时，有效提升了树脂组合物的介电性能；并使预浸料和印制电路用层压板具有优异性能的同时具有优良的尺寸稳定性。(4) The halogen-free flame retardant resin composition provided in the present invention effectively improves the dielectric properties of the resin composition while ensuring that the resin composition has high Tg and high heat resistance; Laminates for printed circuits have excellent performance and excellent dimensional stability.
(5)本发明提供的无卤阻燃型树脂组合物制备得到的层压板的Tg可达200℃以上，介电常数达3.5以下，介电损耗达0.004以下，热分层时间达60min，可通过168h高温高湿测试和冷热冲击循环测试，尺寸稳定性测试中心值达500以下(最好可达300以下)。(5) The Tg of the laminate prepared by the halogen-free flame retardant resin composition provided by the present invention can reach above 200°C, the dielectric constant can reach below 3.5, the dielectric loss can reach below 0.004, and the thermal delamination time can reach 60min. Through 168h high temperature and high humidity test and thermal shock cycle test, the central value of dimensional stability test is below 500 (preferably below 300).
为便于理解本发明，本发明列举实施例如下。本领域技术人员应该明了，所述实施例仅仅是帮助理解本发明，不应视为对本发明的具体限制。In order to facilitate the understanding of the present invention, examples of the present invention are as follows. It should be understood by those skilled in the art that the embodiments are only for helping the understanding of the present invention, and should not be regarded as a specific limitation of the present invention.
以下制备例示例性地提供了端基含有不饱和键的含磷苯并噁嗪树脂的制备方法：The following preparation example exemplarily provides the preparation method of the phosphorus-containing benzoxazine resin whose terminal group contains an unsaturated bond:
制备例1Preparation Example 1
将350g(0.5mol)的OL-1001(购于美国FRX公司，n为3)和1000g适量的甲苯置于三口烧瓶中，向其中加入28.5g(0.5mol)的烯丙胺，75g(1mol)的甲醇水溶液(40％)。加完后以低于2℃/min的升温速率升至90℃，反应5h。然后将温度升至120℃，在小于30tor的压力下，60分钟内将溶剂抽干，并将树脂转移至烧杯中，冰水中冷却得到含磷的不饱和键苯并噁嗪树脂。350g (0.5mol) of OL-1001 (purchased from FRX company in the United States, n is 3) and 1000g of appropriate amount of toluene were placed in a three-necked flask, to which was added 28.5g (0.5mol) of allylamine, 75g (1mol) of Aqueous methanol (40%). After the addition, the temperature was raised to 90°C at a heating rate lower than 2°C/min, and the reaction was carried out for 5h. Then the temperature was raised to 120°C, and the solvent was drained within 60 minutes under a pressure of less than 30tor, and the resin was transferred to a beaker, and cooled in ice water to obtain a phosphorus-containing unsaturated bond benzoxazine resin.
制备例2Preparation Example 2
将400g(0.25mol)的端羟基磷酸酯(购于ICL，n为6)和1000g适量的甲苯置于三口烧瓶中，向其中加入14.25g(0.25mol)的烯丙胺，75g(0.5mol)的甲醇水溶液(40％)。加完后以低于2℃/min的升温速率升至90℃，反应5h。然后将温度升至120℃，在小于30tor的压力下，60分钟内将溶剂抽干，并将树脂转移至烧杯中，冰水中冷却得到含磷的不饱和键苯并噁嗪树脂。400g (0.25mol) of terminal hydroxy phosphate (purchased from ICL, n is 6) and 1000g appropriate amount of toluene were placed in a three-necked flask, 14.25g (0.25mol) of allylamine was added to it, 75g (0.5mol) of Aqueous methanol (40%). After the addition, the temperature was raised to 90°C at a heating rate lower than 2°C/min, and the reaction was carried out for 5h. Then the temperature was raised to 120°C, and the solvent was drained within 60 minutes under a pressure of less than 30tor, and the resin was transferred to a beaker, and cooled in ice water to obtain a phosphorus-containing unsaturated bond benzoxazine resin.
制备例3Preparation Example 3
将370g(0.5mol)的SPH-100(购于日本大塚化学)和1000g适量的甲苯置于三口烧瓶中，向其中加入28.5g(0.5mol)的烯丙胺，75g(1.0mol)的甲醇水溶液(40％)。加完后以低于2℃/min的升温速率升至90℃，反应5h。然后将温度升至120℃，在小于30tor的压力下，60分钟内将溶剂抽干，并将树脂转移至烧杯中，冰水中冷却得到含磷的不饱和键苯并噁嗪树脂。370g (0.5mol) of SPH-100 (purchased from Japan Otsuka Chemical) and 1000g appropriate amount of toluene were placed in a three-necked flask, 28.5g (0.5mol) of allylamine, 75g (1.0mol) of methanol aqueous solution ( 40%). After the addition, the temperature was raised to 90°C at a heating rate lower than 2°C/min, and the reaction was carried out for 5h. Then the temperature was raised to 120°C, and the solvent was drained within 60 minutes under a pressure of less than 30tor, and the resin was transferred to a beaker, and cooled in ice water to obtain a phosphorus-containing unsaturated bond benzoxazine resin.
为更好地说明本发明，便于理解本发明的技术方案，本发明的典型但非限制性的实施例如下：In order to better illustrate the present invention and facilitate the understanding of the technical solutions of the present invention, typical but non-limiting examples of the present invention are as follows:
在所述实施例和对比例中，如无特别说明，其份代表重量份，其％代表“重 量％”。In the Examples and Comparative Examples, unless otherwise specified, parts represent parts by weight, and % represent "% by weight".
实施例和对比例涉及的材料及牌号信息如下：The materials and trade mark information involved in embodiment and comparative example are as follows:
(A)环氧树脂：(A) Epoxy resin:
A1：购于日本DIC的型号为HP-7200H-75M的DCPD型环氧树脂，环氧当量270；A1: DCPD type epoxy resin with model HP-7200H-75M purchased from DIC in Japan, epoxy equivalent 270;
A2：购于日本化药的型号为NC-3000H的联苯型环氧树脂，环氧当量290；A2: Biphenyl epoxy resin with model NC-3000H purchased from Nippon Kayaku, epoxy equivalent 290;
A3：购于长春人造树脂厂的型号为TFE-1250的三官能环氧树脂，环氧当量215；A3: Trifunctional epoxy resin with model TFE-1250 purchased from Changchun Artificial Resin Factory, epoxy equivalent of 215;
(B-1)端基含有不饱和键的含磷苯并噁嗪树脂(B-1) Phosphorus-containing benzoxazine resin whose terminal group contains unsaturated bond
B-11：制备例1得到的端基含有不饱和键的含磷苯并噁嗪树脂(OL1001)；B-11: Phosphorus-containing benzoxazine resin (OL1001) containing an unsaturated bond in the terminal group obtained in Preparation Example 1;
B-12：制备例2得到的端基含有不饱和键的含磷苯并噁嗪树脂(PMP)；B-12: Phosphorus-containing benzoxazine resin (PMP) containing an unsaturated bond in the terminal group obtained in Preparation Example 2;
B-13：制备例3得到的端基含有不饱和键的含磷苯并噁嗪树脂(SPH100)；B-13: Phosphorus-containing benzoxazine resin (SPH100) containing an unsaturated bond in the terminal group obtained in Preparation Example 3;
(B-2)苯并噁嗪树脂(B-2) Benzoxazine resin
B-21：KOLON的KZH-5031；B-21: KZH-5031 of KOLON;
B-22：ODA型苯并噁嗪树脂D129，购自四川东材科技；B-22: ODA type benzoxazine resin D129, purchased from Sichuan Dongcai Technology;
B-23：CN103421192A中公开的含磷苯并噁嗪树脂(9-BZ)；B-23: Phosphorus-containing benzoxazine resin (9-BZ) disclosed in CN103421192A;
(C)马来酰亚胺化合物(C) Maleimide compound
C1：购于日本KI CHEMICAL的型号为BMI-70的3,3'-二甲基-5,5'-二乙基-4,4'-二苯基甲烷双马来酰亚胺；C1: 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, model BMI-70, purchased from KI CHEMICAL in Japan;
C2：购于四川东材科技的D950的改性马来酰亚胺；C2: D950 modified maleimide purchased from Sichuan Dongcai Technology;
(D)阻燃剂(D) Flame Retardant
D1：购于日本大塚化学株式会社的型号为SPB-100的产品；D1: Product model SPB-100 purchased from Otsuka Chemical Co., Ltd., Japan;
D2：购于日本大八化学的型号为PX-200的产品；D2: The product of model PX-200 purchased from Japan's Daiba Chemical;
(E)填料(E) Packing
E1：购于江苏联瑞新材料股份有限公司的球形二氧化硅NQ2025W；E1: Spherical silica NQ2025W purchased from Jiangsu Lianrui New Materials Co., Ltd.;
E2：购于美国特矿的滑石粉AG-609；E2: Talc powder AG-609 purchased from U.S. Special Mine;
(F)聚苯醚树脂(F) Polyphenylene ether resin
F1：购于SABIC公司的型号为SA-9000的甲基丙烯酸酯封端的聚苯醚树脂F1: methacrylate-terminated polyphenylene ether resin, model SA-9000, purchased from SABIC
F2：购于SABIC公司的型号为SA-90的羟基封端的聚苯醚树脂F2: Hydroxy-terminated polyphenylene ether resin, model SA-90, purchased from SABIC
(G)活性酯树脂(G) Active ester resin
G1：购于日本DIC公司的型号为HPC-8000-65T的活性酯树脂G1: Active ester resin with model HPC-8000-65T purchased from DIC Corporation of Japan
G2：购于日本DIC公司的型号为HPC-8150-62T的活性酯树脂G2: Active ester resin with model HPC-8150-62T purchased from DIC Corporation of Japan
(H)固化促进剂(H) Curing accelerator
H1：购于日本四国化成的2-乙基-4-甲基咪唑。H1: 2-ethyl-4-methylimidazole purchased from Shikoku Chemicals, Japan.
将以下表1和表2中所示的实施例和对比例提供的树脂组合物，按照如下方法制备印制电路用层压板，并对制备得到的层压板进行性能测试。The resin compositions provided in the Examples and Comparative Examples shown in Table 1 and Table 2 below were used to prepare laminates for printed circuits according to the following method, and the performance tests were carried out on the prepared laminates.
所述印制电路用层压板的制备方法包括：The preparation method of the printed circuit laminate comprises:
①通过加热和加压作用分别使上述实施例和对比例的树脂组合物制备得到的预浸料粘合在一起，制成的层压板；①A laminate made by bonding the prepregs prepared from the resin compositions of the above examples and comparative examples by heating and pressing, respectively;
②在步骤①制得的层压板的两面上粘合金属箔；② Adhere metal foils on both sides of the laminate obtained in step ①;
③在层压机中进行层压；③ Laminate in a laminator;
在步骤①和②的过程中，使用8片预浸料和2片一盎司(35μm厚)的铜箔 叠合在一起；During steps ① and ②, use 8 pieces of prepreg and 2 pieces of one ounce (35μm thick) copper foil to be laminated together;
在步骤③的过程中，层压的操作条件为：料温100℃，控制升温速率为2.3℃/min；外层料温90℃，施加满压，满压压力为350psi；固化时，控制料温在210℃，并保温120min以上。In the process of step (3), the operating conditions of lamination are: the material temperature is 100°C, and the heating rate is controlled to be 2.3°C/min; the material temperature of the outer layer is 90°C, and the full pressure is applied, and the full pressure is 350 psi; during curing, the material is controlled to Temperature at 210 ℃, and keep warm for more than 120min.
实施例和对比例提供的树脂组合物的配方及性能测试结果见表1和表2。The formulations and performance test results of the resin compositions provided in Examples and Comparative Examples are shown in Table 1 and Table 2.
表1Table 1
表2Table 2
上述表格中，冷热冲击循环测试结果中“未通过”代表板材在冷热冲击循环测试中出现鼓泡，分层等缺陷；168h高温高湿测试中“失败”代表板材在经过高温高湿处理168小时后进行浸锡测试时，在300秒内出现了鼓泡，分层等缺陷，“通过”代表未出现前述缺陷。In the above table, "failed" in the cold and thermal shock cycle test results means that the plate has defects such as bubbling and delamination in the cold and heat shock cycle test; "failed" in the 168h high temperature and high humidity test means that the plate has undergone high temperature and high humidity treatment. When the immersion tin test was performed after 168 hours, defects such as bubbling and delamination appeared within 300 seconds, and "pass" means that the aforementioned defects did not appear.
由表1至表3所示的数据可知，本发明通过在树脂组合物配方中添加端基含有不饱和键的含磷苯并噁嗪树脂，能够在保证树脂组合物具有高Tg、高耐热性的同时，有效提升了树脂组合物的介电性能；并使预浸料和印制电路用层压板具有优异性能的同时具有优良的尺寸稳定性、耐高温高湿性和耐冷热冲击性。无论是将端基含有不饱和键的含磷苯并噁嗪树脂替换为其他的树脂(对比例2-4)，还是改变配方内各组分的比例(对比例1、5、6、7和8)，均会使产品的综合性能下降。From the data shown in Tables 1 to 3, it can be seen that the present invention can ensure that the resin composition has high Tg, high heat resistance by adding phosphorus-containing benzoxazine resins containing unsaturated bonds at the end groups to the resin composition formulation. At the same time, the dielectric properties of the resin composition are effectively improved; and the prepreg and printed circuit laminates have excellent properties, as well as excellent dimensional stability, high temperature and high humidity resistance and thermal shock resistance. Whether it is to replace the phosphorus-containing benzoxazine resin with unsaturated bonds at the end group with other resins (Comparative Examples 2-4), or to change the ratio of each component in the formulation (Comparative Examples 1, 5, 6, 7 and 8), which will reduce the overall performance of the product.
本发明提供的树脂组合物在尺寸稳定性测试中，树脂收缩值均小于500ppm极大降低了生产控制难度，有利于提升下游产品的良率、降低报废比率。In the dimensional stability test of the resin composition provided by the invention, the resin shrinkage value is less than 500ppm, which greatly reduces the difficulty of production control, is beneficial to improve the yield of downstream products and reduce the scrap ratio.
性能测试的项目及具体方法为：The items and specific methods of performance testing are:
(a)玻璃化转变温度：(a) Glass transition temperature:
根据差示扫描量热法，按照IPC-TM-650中所规定的TMA方法进行测定。According to differential scanning calorimetry, it measured according to the TMA method prescribed|regulated by IPC-TM-650.
(b)耐燃烧性：(b) Fire resistance:
依据UL94法测定。Determined according to UL94 method.
(c)吸水性：(c) Water absorption:
按照IPC-TM-650中的2.6.2.1所规定的方法进行测定。Measure according to the method specified in 2.6.2.1 of IPC-TM-650.
(d)介电常数和介电损耗因素(d) Dielectric constant and dielectric loss factor
根据使用条状线的共振法，按照IPC-TM-650中的2.5.5.5所规定的方法测定1GHz下的介电常数和介电损耗因素。The dielectric constant and dielectric loss factor at 1 GHz were measured according to the method specified in 2.5.5.5 of IPC-TM-650 by the resonance method using the strip line.
(e)热分层时间T288(e) Thermal delamination time T288
根据IPC-TM-650中的2.4.24.1所规定的方法进行测定，单位：分钟。Measured according to the method specified in 2.4.24.1 of IPC-TM-650, unit: minute.
(f)168h高温高湿测试(f) 168h high temperature and high humidity test
根据IPC-TM-650。According to IPC-TM-650.
(g)冷热冲击循环1000cycle(g) 1000 cycle of thermal shock cycle
制作1.00mm厚度的板材。一个冷热冲击循环是指:从室温以5℃/min降温至-40℃，然后以5℃/min升温速率升温到120℃，保持10min后，再按5℃/min降温速率降到室温。A sheet of 1.00mm thickness is produced. A thermal shock cycle refers to: cooling from room temperature to -40°C at a rate of 5°C/min, then heating up to 120°C at a heating rate of 5°C/min, holding for 10 minutes, and then dropping to room temperature at a cooling rate of 5°C/min.
(h)尺寸稳定性测试(中心值)(h) Dimensional stability test (center value)
根据IPC-TM-650中所规定的方法测试。使用0.076mm厚度板材，测试其在150℃烘烤后的尺寸变化数据，取至少6组数据的中心值的绝对值，单位：ppm。Tested according to the method specified in IPC-TM-650. Use a 0.076mm thick plate to test its dimensional change data after baking at 150°C, and take the absolute value of the central value of at least 6 sets of data, unit: ppm.
申请人声明，本发明通过上述实施例来说明本发明的详细工艺设备和工艺流程，但本发明并不局限于上述详细工艺设备和工艺流程，即不意味着本发明必须依赖上述详细工艺设备和工艺流程才能实施。所属技术领域的技术人员应该明了，对本发明的任何改进，对本发明产品各原料的等效替换及辅助成分的添加、具体方式的选择等，均落在本发明的保护范围和公开范围之内。The applicant declares that the present invention illustrates the detailed process equipment and process flow of the present invention through the above-mentioned embodiments, but the present invention is not limited to the above-mentioned detailed process equipment and process flow, that is, it does not mean that the present invention must rely on the above-mentioned detailed process equipment and process flow. Process flow can be implemented. Those skilled in the art should understand that any improvement to the present invention, the equivalent replacement of each raw material of the product of the present invention, the addition of auxiliary components, the selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.
Claims (10)
- 一种无卤阻燃型树脂组合物，其特征在于，以固体组分重量份计，包括如下组分：A halogen-free flame retardant resin composition, characterized in that, in parts by weight of solid components, it comprises the following components:(A)环氧树脂：1～40重量份；(A) epoxy resin: 1 to 40 parts by weight;(B)端基含有不饱和键的含磷苯并噁嗪树脂：1～30重量份；(B) Phosphorus-containing benzoxazine resin whose terminal group contains unsaturated bonds: 1 to 30 parts by weight;(C)马来酰亚胺化合物：30～80重量份。(C) Maleimide compound: 30 to 80 parts by weight.
- 如权利要求1所述的无卤阻燃型树脂组合物，其特征在于，所述的环氧树脂(A)选自双环戊二烯环氧树脂、含磷环氧树脂、异氰酸酯改性环氧树脂、联苯环氧树脂、双酚A型环氧树脂、苯酚型酚醛环氧树脂、邻甲酚醛型环氧树脂、环氧化聚丁二烯树脂、含萘环的环氧树脂、双酚F型环氧树脂、三官能环氧树脂、氢化的双酚A环氧树脂或氢化的双酚F型环氧中的任意一种或至少两种的组合；The halogen-free flame retardant resin composition according to claim 1, wherein the epoxy resin (A) is selected from the group consisting of dicyclopentadiene epoxy resin, phosphorus-containing epoxy resin, and isocyanate modified epoxy resin Resin, biphenyl epoxy resin, bisphenol A epoxy resin, phenol novolac epoxy resin, o-cresol novolac epoxy resin, epoxidized polybutadiene resin, epoxy resin containing naphthalene ring, bisphenol Any one or a combination of at least two of F-type epoxy resins, trifunctional epoxy resins, hydrogenated bisphenol A epoxy resins or hydrogenated bisphenol F-type epoxy resins;优选地，所述的树脂组合物中，环氧树脂(A)的含量为5～30重量份。Preferably, in the resin composition, the content of the epoxy resin (A) is 5-30 parts by weight.
- 如权利要求1或2所述的无卤阻燃型树脂组合物，其特征在于，所述的端基含有不饱和键的含磷苯并噁嗪树脂(B)，其结构如下式：The halogen-free flame-retardant resin composition according to claim 1 or 2, characterized in that, the phosphorus-containing benzoxazine resin (B) whose terminal group contains an unsaturated bond has the following structure:Q为取代或未取代的含不饱和键的基团；Q is a substituted or unsubstituted unsaturated bond-containing group;X为X is其中m为重复单元数量的平均值，为3～10的任意数；n为重复单元数量的 平均值，为0～10的任意数；Wherein m is the average value of the number of repeating units, which is any number from 3 to 10; n is the average value of the number of repeating units, which is any number from 0 to 10;R 1为H、C1～C4的直链或支链烷烃、取代或未取代的芳基、取代或未取代的芳氧基中的一种； R 1 is one of H, C1-C4 straight-chain or branched alkane, substituted or unsubstituted aryl, and substituted or unsubstituted aryloxy;Y选自下列结构：Y is selected from the following structures:Z为共价键或选自下列结构：Z is a covalent bond or is selected from the following structures:优选地，Q为固化后形成疏水性链段的基团，进一步优选为取代或未取代的C2-C10烯基、取代或未取代的苯乙烯基、取代或未取代的丙烯酸酯基团中的 一种，更优选为取代或未取代的乙烯基、取代或未取代的烯丙基、取代或未取代的苯乙烯基、取代或未取代的含有苯基的丙烯酸酯基中的一种；Preferably, Q is a group that forms a hydrophobic segment after curing, more preferably a substituted or unsubstituted C2-C10 alkenyl group, a substituted or unsubstituted styryl group, and a substituted or unsubstituted acrylate group One, more preferably one of substituted or unsubstituted vinyl, substituted or unsubstituted allyl, substituted or unsubstituted styryl, substituted or unsubstituted phenyl-containing acrylate group;优选地，所述端基含有不饱和含磷苯并噁嗪树脂由含磷元素的二酚化合物、含不饱和键的胺类化合物和甲醇通过反应而得。Preferably, the end group-containing unsaturated phosphorus-containing benzoxazine resin is obtained by reacting a phosphorus-containing diphenol compound, an unsaturated bond-containing amine compound and methanol.
- 根据权利要求3所述的无卤阻燃型树脂组合物，其特征在于，所述端基含有不饱和含磷苯并噁嗪树脂选自式(a)、式(b)中的一种或至少两种的组合：The halogen-free flame retardant resin composition according to claim 3, wherein the terminal group contains unsaturated phosphorus-containing benzoxazine resin selected from one of formula (a), formula (b) or A combination of at least two:式(a)、式(b)中，所述m、n、R 1、Q、Z和Y均具有与式(B)中相同的限定范围； In formula (a) and formula (b), the m, n, R 1 , Q, Z and Y all have the same limited range as in formula (B);优选地，式(a)选自如下式(a1)、(a2)或(a3)中的至少一种或两种及其以上的组合：Preferably, formula (a) is selected from at least one of the following formulas (a1), (a2) or (a3) or a combination of two or more thereof:式(a1)至(a3)中所述Q具有与式(B)中相同的限定范围；Q described in formulas (a1) to (a3) has the same defined range as in formula (B);优选地，式(b)选自如下式(b1)、(b2)、(b3)、(b4)或(b5)中的至少一种或两种及其以上的组合：Preferably, formula (b) is selected from at least one of the following formulas (b1), (b2), (b3), (b4) or (b5) or a combination of two or more thereof:式(b1)至(b5)中，所述n和Q均具有与式(B)中相同的限定范围。In the formulae (b1) to (b5), both of the n and Q have the same defined ranges as in the formula (B).
- 如权利要求1～4之一所述的树脂组合物，其特征在于，所述的树脂组合物中，所述的马来酰亚胺化合物(C)选自4,4'-二苯甲烷双马来酰亚胺、聚苯甲烷马来酰亚胺、间-伸苯基双马来酰亚胺、双酚A二苯基醚双马来酰亚胺、3,3'-二甲基-5,5'-二乙基-4,4'-二苯基甲烷双马来酰亚胺、4-甲基-1,3-伸苯基双马来酰亚胺、1,6-双马来酰亚胺-(2,2,4-三甲基)己烷、2,3-二甲基苯马来酰亚胺、2,6-二甲基苯马来酰亚胺、N-苯基马来酰亚胺、含脂肪族长链结构的马来酰亚胺、烯 丙基化合物改性马来酰亚胺、胺类改性马来酰亚胺或酸性酚化合物改性马来酰亚胺中的任意一种或至少两种的组合；The resin composition according to any one of claims 1 to 4, wherein in the resin composition, the maleimide compound (C) is selected from 4,4'-diphenylmethanebis Maleimide, polyphenylene methane maleimide, m-phenylene bismaleimide, bisphenol A diphenyl ether bismaleimide, 3,3'-dimethyl- 5,5'-Diethyl-4,4'-diphenylmethane bismaleimide, 4-methyl-1,3-phenylene bismaleimide, 1,6-bismaleimide Leimide-(2,2,4-trimethyl)hexane, 2,3-dimethylbenzenemaleimide, 2,6-dimethylbenzenemaleimide, N-benzene base maleimide, maleimide containing aliphatic long chain structure, allyl compound modified maleimide, amine modified maleimide or acid phenol compound modified maleimide any one or a combination of at least two of the amines;优选地，所述的树脂组合物中，马来酰亚胺化合物(C)的含量为35～70重量份；Preferably, in the resin composition, the content of the maleimide compound (C) is 35-70 parts by weight;优选地，所述的树脂组合物中，还包含阻燃剂(D)；Preferably, the resin composition further comprises a flame retardant (D);优选地，所述的阻燃剂(D)选自间苯二酚-双(磷酸二苯酯)、双酚A-双(磷酸二苯酯)、间苯二酚-双(2,6-二甲苯基磷酸酯)、甲基磷酸二甲酯、添加型磷腈化合物或反应型磷腈化合物中的任意一种或至少两种的组合；Preferably, the flame retardant (D) is selected from resorcinol-bis(diphenyl phosphate), bisphenol A-bis(diphenyl phosphate), resorcinol-bis(2,6- Any one or a combination of at least two of xylyl phosphate), dimethyl methyl phosphate, additive phosphazene compound or reactive phosphazene compound;优选地，所述的树脂组合物中，阻燃剂(D)的含量为0.1～15重量份；Preferably, in the resin composition, the content of the flame retardant (D) is 0.1-15 parts by weight;优选地，所述的树脂组合物中，还包含填料(E)；Preferably, the resin composition further comprises filler (E);优选地，所述的填料(E)选自氢氧化铝、二氧化硅、石粉、勃姆石、沸石、硅灰石、氧化镁、硅酸钙、碳酸钙、粘土或云母中的任意一种或至少两种的组合；Preferably, the filler (E) is selected from any one of aluminum hydroxide, silica, stone powder, boehmite, zeolite, wollastonite, magnesium oxide, calcium silicate, calcium carbonate, clay or mica or a combination of at least two;优选地，所述的树脂组合物中，填料(E)的含量为10～250重量份。Preferably, in the resin composition, the content of the filler (E) is 10-250 parts by weight.
- 如权利要求1～5之一所述的无卤阻燃型树脂组合物，其特征在于，所述的树脂组合物中，还包含聚苯醚树脂(F)；The halogen-free flame-retardant resin composition according to any one of claims 1 to 5, wherein the resin composition further comprises a polyphenylene ether resin (F);优选地，所述的聚苯醚树脂(F)选自羟基封端的聚苯醚和/或不饱和双键封端的聚苯醚树脂；Preferably, the polyphenylene ether resin (F) is selected from hydroxyl-terminated polyphenylene ether and/or unsaturated double bond-terminated polyphenylene ether resin;优选地，所述的树脂组合物中，聚苯醚树脂(F)的含量为0.1～30重量份；Preferably, in the resin composition, the content of the polyphenylene ether resin (F) is 0.1 to 30 parts by weight;优选地，所述的树脂组合物中，还包括活性酯树脂(G)；Preferably, the resin composition further comprises active ester resin (G);优选地，所述的树脂组合物中，活性酯树脂(G)的含量为0.1～30重量份；Preferably, in the resin composition, the content of the active ester resin (G) is 0.1-30 parts by weight;优选地，所述的树脂组合物中，还包含固化促进剂(H)；Preferably, the resin composition further comprises a curing accelerator (H);优选地，所述的固化促进剂选自咪唑类促进剂及其衍生物、吡啶类、路易 斯酸类、胺类、酚醛类或氰酸酯类化合物中的任意一种或至少两种的组合；Preferably, the curing accelerator is selected from any one or a combination of at least two of imidazole accelerators and derivatives thereof, pyridines, Lewis acids, amines, phenolic compounds or cyanate ester compounds;优选地，所述的树脂组合物中，固化促进剂(H)的含量为0.1～5重量份。Preferably, in the resin composition, the content of the curing accelerator (H) is 0.1-5 parts by weight.
- 一种预浸料、树脂膜或涂树脂铜箔，其特征在于，所述预浸料、树脂膜或涂树脂铜箔包括权利要求1～6之一所述的无卤阻燃型树脂组合物；A prepreg, resin film or resin-coated copper foil, characterized in that the prepreg, resin film or resin-coated copper foil comprises the halogen-free flame retardant resin composition according to any one of claims 1 to 6 ;优选地，所述的预浸料包括基料和附着在所述基料上的所述无卤阻燃型树脂组合物；Preferably, the prepreg comprises a base material and the halogen-free flame retardant resin composition attached to the base material;优选地，所述的预浸料包括基料及通过含浸和干燥处理后附着在所述基料上的所述无卤阻燃型树脂组合物。Preferably, the prepreg material includes a base material and the halogen-free flame retardant resin composition adhered to the base material after impregnation and drying treatment.
- 一种绝缘板，其特征在于，所述绝缘板包括至少一张权利要求7所述的预浸料。An insulating board, characterized in that the insulating board comprises at least one prepreg according to claim 7 .
- 一种覆金属箔层压板，其特征在于，所述覆金属箔层压板包括至少一张权利要求7所述的预浸料以及覆于叠合后的预浸料一侧或两侧的金属箔。A metal foil clad laminate, characterized in that the metal foil clad laminate comprises at least one prepreg according to claim 7 and metal foils covering one or both sides of the laminated prepreg .
- 一种印刷电路板，其特征在于，所述印刷电路板包括至少一张权利要求7所述的预浸料，或至少一张权利要求8所述的绝缘板，或至少一张权利要求9所述的覆金属箔层压板。A PCB Metal-clad laminates described above.
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