CN107201037B - Resin combination and prepreg, metal foil laminate and the interlayer dielectric made using it - Google Patents
Resin combination and prepreg, metal foil laminate and the interlayer dielectric made using it Download PDFInfo
- Publication number
- CN107201037B CN107201037B CN201710561169.8A CN201710561169A CN107201037B CN 107201037 B CN107201037 B CN 107201037B CN 201710561169 A CN201710561169 A CN 201710561169A CN 107201037 B CN107201037 B CN 107201037B
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- China
- Prior art keywords
- resin
- parts
- bismaleimide
- diamine
- benzoxazine
- Prior art date
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- 229920005989 resin Polymers 0.000 title claims abstract description 125
- 239000011347 resin Substances 0.000 title claims abstract description 125
- 229910052751 metal Inorganic materials 0.000 title claims description 26
- 239000002184 metal Substances 0.000 title claims description 26
- 239000011888 foil Substances 0.000 title claims description 18
- 239000011229 interlayer Substances 0.000 title claims description 9
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 claims abstract description 64
- CMLFRMDBDNHMRA-UHFFFAOYSA-N 2h-1,2-benzoxazine Chemical compound C1=CC=C2C=CNOC2=C1 CMLFRMDBDNHMRA-UHFFFAOYSA-N 0.000 claims abstract description 56
- 239000003822 epoxy resin Substances 0.000 claims abstract description 42
- 229920003192 poly(bis maleimide) Polymers 0.000 claims abstract description 42
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 42
- -1 diamines modified bismaleimide Chemical class 0.000 claims abstract description 35
- 150000004985 diamines Chemical class 0.000 claims abstract description 27
- 239000007787 solid Substances 0.000 claims abstract description 23
- 239000011342 resin composition Substances 0.000 claims description 30
- 239000002904 solvent Substances 0.000 claims description 20
- 229920001955 polyphenylene ether Polymers 0.000 claims description 16
- 239000003063 flame retardant Substances 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 13
- 239000003292 glue Substances 0.000 claims description 11
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims description 10
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- 239000003960 organic solvent Substances 0.000 claims description 8
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000011256 inorganic filler Substances 0.000 claims description 7
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 7
- 229920013636 polyphenyl ether polymer Polymers 0.000 claims description 7
- 229920013638 modified polyphenyl ether Polymers 0.000 claims description 6
- 239000012779 reinforcing material Substances 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 239000004593 Epoxy Substances 0.000 claims description 4
- 239000011230 binding agent Substances 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 claims description 3
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 3
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- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 7
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 7
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 7
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- 239000011574 phosphorus Substances 0.000 description 7
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- 229910052802 copper Inorganic materials 0.000 description 6
- 239000010949 copper Substances 0.000 description 6
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 150000001412 amines Chemical class 0.000 description 5
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 4
- 229910052794 bromium Inorganic materials 0.000 description 4
- 239000011889 copper foil Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 239000004843 novolac epoxy resin Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000010561 standard procedure Methods 0.000 description 4
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 3
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 3
- XLLIQLLCWZCATF-UHFFFAOYSA-N 2-methoxyethyl acetate Chemical compound COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 description 3
- QMAQLCVJIYANPZ-UHFFFAOYSA-N 2-propoxyethyl acetate Chemical compound CCCOCCOC(C)=O QMAQLCVJIYANPZ-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 3
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical group CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
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- 238000002474 experimental method Methods 0.000 description 3
- 239000003365 glass fiber Substances 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 150000002460 imidazoles Chemical group 0.000 description 3
- 239000012948 isocyanate Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
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- 239000008096 xylene Substances 0.000 description 3
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 2
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 2
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 2
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical group CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
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- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- DYIZJUDNMOIZQO-UHFFFAOYSA-N 4,5,6,7-tetrabromo-2-[2-(4,5,6,7-tetrabromo-1,3-dioxoisoindol-2-yl)ethyl]isoindole-1,3-dione Chemical compound O=C1C(C(=C(Br)C(Br)=C2Br)Br)=C2C(=O)N1CCN1C(=O)C2=C(Br)C(Br)=C(Br)C(Br)=C2C1=O DYIZJUDNMOIZQO-UHFFFAOYSA-N 0.000 description 1
- WOCGGVRGNIEDSZ-UHFFFAOYSA-N 4-[2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical compound C=1C=C(O)C(CC=C)=CC=1C(C)(C)C1=CC=C(O)C(CC=C)=C1 WOCGGVRGNIEDSZ-UHFFFAOYSA-N 0.000 description 1
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical group CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 1
- OEOIWYCWCDBOPA-UHFFFAOYSA-N 6-methyl-heptanoic acid Chemical compound CC(C)CCCCC(O)=O OEOIWYCWCDBOPA-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 239000004114 Ammonium polyphosphate Substances 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- KYNSBQPICQTCGU-UHFFFAOYSA-N Benzopyrane Chemical compound C1=CC=C2C=CCOC2=C1 KYNSBQPICQTCGU-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- 229920002799 BoPET Polymers 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- YBUPZEKLPLIZNR-UHFFFAOYSA-N C.C(C)C=1C=CC=C(C1N1C(C=CC1=O)=O)C.C(C)C=1C=CC=C(C1N1C(C=CC1=O)=O)C Chemical compound C.C(C)C=1C=CC=C(C1N1C(C=CC1=O)=O)C.C(C)C=1C=CC=C(C1N1C(C=CC1=O)=O)C YBUPZEKLPLIZNR-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- OWIKHYCFFJSOEH-UHFFFAOYSA-N Isocyanic acid Chemical class N=C=O OWIKHYCFFJSOEH-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 229920000388 Polyphosphate Polymers 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- VMCRDONCOBHEHW-UHFFFAOYSA-N [2,6-bis(2,6-dimethylphenyl)phenyl]phosphane Chemical compound CC1=CC=CC(C)=C1C1=CC=CC(C=2C(=CC=CC=2C)C)=C1P VMCRDONCOBHEHW-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- DHAHRLDIUIPTCJ-UHFFFAOYSA-K aluminium metaphosphate Chemical compound [Al+3].[O-]P(=O)=O.[O-]P(=O)=O.[O-]P(=O)=O DHAHRLDIUIPTCJ-UHFFFAOYSA-K 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 235000019826 ammonium polyphosphate Nutrition 0.000 description 1
- 229920001276 ammonium polyphosphate Polymers 0.000 description 1
- 229910052454 barium strontium titanate Inorganic materials 0.000 description 1
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 1
- 229910002113 barium titanate Inorganic materials 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 150000005130 benzoxazines Chemical class 0.000 description 1
- APOXBWCRUPJDAC-UHFFFAOYSA-N bis(2,6-dimethylphenyl) hydrogen phosphate Chemical compound CC1=CC=CC(C)=C1OP(O)(=O)OC1=C(C)C=CC=C1C APOXBWCRUPJDAC-UHFFFAOYSA-N 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 description 1
- 150000007973 cyanuric acids Chemical class 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 description 1
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- JDVIRCVIXCMTPU-UHFFFAOYSA-N ethanamine;trifluoroborane Chemical compound CCN.FB(F)F JDVIRCVIXCMTPU-UHFFFAOYSA-N 0.000 description 1
- JHXRVOAOESLJHL-UHFFFAOYSA-N ethene;1,2,3,4,5-pentabromobenzene Chemical compound C=C.BrC1=CC(Br)=C(Br)C(Br)=C1Br.BrC1=CC(Br)=C(Br)C(Br)=C1Br JHXRVOAOESLJHL-UHFFFAOYSA-N 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 238000005213 imbibition Methods 0.000 description 1
- 125000005462 imide group Chemical group 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- PSHKMPUSSFXUIA-UHFFFAOYSA-N n,n-dimethylpyridin-2-amine Chemical compound CN(C)C1=CC=CC=N1 PSHKMPUSSFXUIA-UHFFFAOYSA-N 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
- 125000005609 naphthenate group Chemical group 0.000 description 1
- 150000004780 naphthols Chemical class 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- WWZKQHOCKIZLMA-UHFFFAOYSA-M octanoate Chemical compound CCCCCCCC([O-])=O WWZKQHOCKIZLMA-UHFFFAOYSA-M 0.000 description 1
- AHLBNYSZXLDEJQ-FWEHEUNISA-N orlistat Chemical compound CCCCCCCCCCC[C@H](OC(=O)[C@H](CC(C)C)NC=O)C[C@@H]1OC(=O)[C@H]1CCCCCC AHLBNYSZXLDEJQ-FWEHEUNISA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229950000688 phenothiazine Drugs 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 description 1
- 238000011179 visual inspection Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- XAEWLETZEZXLHR-UHFFFAOYSA-N zinc;dioxido(dioxo)molybdenum Chemical compound [Zn+2].[O-][Mo]([O-])(=O)=O XAEWLETZEZXLHR-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/12—Unsaturated polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/12—Unsaturated polyimide precursors
- C08G73/124—Unsaturated polyimide precursors the unsaturated precursors containing oxygen in the form of ether bonds in the main chain
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/12—Unsaturated polyimide precursors
- C08G73/128—Unsaturated polyimide precursors the unsaturated precursors containing heterocyclic moieties in the main chain
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Laminated Bodies (AREA)
Abstract
The invention discloses a kind of resin combinations, with solid weight meter, comprising: the diamines modified bismaleimide resin of (a) structure containing benzoxazine: 40 ~ 80 parts；(b) epoxy resin: 10 ~ 50 parts；(c) polyphenylene oxide: 10 ~ 40 parts.The present invention passes through bismaleimide and the pre-reaction preferential at low temperature of the diamine resin containing benzoxazine, and open loop does not almost occur for benzoxazine under low temperature；A part of reactive group is consumed by pre-reaction, form the prepolymer with certain molecular weight, increase the steric hindrance of benzoxazine ring-opening reaction, slowed down benzoxazine structure in resin structure reaction rate, the rheology Process window for having adjusted resin combination well reduces resin combination and the risk of the defect of substrate dried flower or lineae ablicantes occurs because reacting too fast during the pressing process.
Description
Technical Field
The invention relates to a resin composition, and a prepreg, a metal foil laminated board and an interlayer insulating film which are manufactured by using the resin composition, and belongs to the technical field of electronic materials.
Background
The progress of electronic technology is changing day by day, and portability and lightness and thinness become the direction that electronic complete machine products are always sought, and the lightness and thinness of the complete machine products need to prepare electronic products including printed circuit boards, so that copper-clad plate base materials are required to have higher rigidity and anti-warping capability so as to meet the requirements of structural support and processing procedures of the printed circuit boards.
In the prior art, polyphenylene oxide resin has excellent water resistance, dimensional stability, flame retardant property and dielectric property, and is mixed with other materials to obtain a resin composition with more excellent comprehensive properties. Although the copper foil laminated board based on the polyphenyl ether resin can obtain excellent dielectric property, in the application of the prior art, because the polyphenyl ether resin has lower polarity and poorer compatibility with other resins in the resin composition, the appearance of the prepreg is further influenced; further, the impregnation property between the polyphenylene ether resin and the glass cloth is not satisfactory, and the polyphenylene ether resin tends to form a thin film on the surface of the glass cloth, which also affects the appearance of the prepreg and adversely affects the dielectric properties of the product. Chinese patent publication No. CN1556830A proposes a method for functionalizing polyphenylene ether, i.e., polyphenylene ether and epoxy resin are reacted under the action of an amine catalyst to obtain a polyphenylene ether/epoxy resin prepolymer having two epoxy groups at two end groups, which improves the above-mentioned application problem of polyphenylene ether to a certain extent, but the introduced epoxy resin has an adverse effect on the dielectric properties of resin molecules to increase Dk/Df.
On the other hand, among the existing resin materials for manufacturing printed circuit boards, bismaleimide is one of the excellent resins, and is a thermosetting resin containing an imide structure, and the high crosslinking density after curing makes the resin have high glass transition temperature, excellent thermal stability and higher rigidity, and is one of the first materials for manufacturing thin substrates at present. However, bismaleimide monomers have the disadvantages of high melting point, poor solubility, high curing reaction temperature, and high brittleness of the cured resin, which limits the application thereof.
In view of the above technical problems, currently, there are two mature technical routes for modifying bismaleimide resins with allyl compounds or aromatic diamine compounds, such as the series of Kerimid resins introduced by Huntsman corporation in the last century, and the series of allyl compounds modified bismaleimide resins developed by professor in the western university of industry, and the obtained modified bismaleimide resins have excellent properties such as high toughness, excellent solubility (solubility in organic solvents such as acetone/butanone), high glass transition temperature, and the like.
However, although the above 2 technical solutions can solve the problems of solubility and toughness of the resin well, the problem of high water absorption of the imide group inherent in the bismaleimide resin is still not solved, which brings some problems to the application of the bismaleimide resin in the field of electronic circuits, and when the modified bismaleimide resin (usually modified by allyl or diamine) in the formulation of the copper clad laminate resin as the substrate for preparing the electronic circuit is high in component, the water absorption of the substrate is often large, which results in high warpage rate of the substrate after absorbing water. In addition, the high water absorption rate not only easily causes corrosion of the metal connector in a humid environment, but also causes the expansion and shrinkage of the metal connector after being manufactured into a thin plate and the warpage rate to be increased, thereby greatly influencing the manufacturing process of the printed circuit board. Therefore, how to reduce the water absorption of the bismaleimide resin and reduce the warpage rate of the bismaleimide resin after being made into a thin plate while modifying the bismaleimide resin becomes one of the difficulties in the application of the bismaleimide resin in the field of electronic circuits.
The bismaleimide triazine resin (BT resin) of Mitsubishi gas is a model of bismaleimide and cyanate application, successfully solves the problem of water absorption of bismaleimide resin application, and has a patent technology disclosed, but key technical points of the bismaleimide triazine resin are still difficult to master by technicians in China.
Chinese patent application CN104725781A discloses a composition of amine modified bismaleimide resin, benzoxazine resin and epoxy resin, although it reduces the water absorption of bismaleimide. However, the applicant has carried out experiments to find that: the amine modified bismaleimide resin can effectively improve the reactivity of benzoxazine (which is also described in 'BMI modified benzoxazine resin and composite material research' of Li Ling et al), and the rheological window of the amine modified bismaleimide resin in the pressing process is narrowed, so that certain risks of drying flowers and white lines are caused to the secondary appearance of a copper-clad plate substrate.
The inventors have made extensive studies on the above phenomenon, and the reason is considered as follows: the amine modified bismaleimide resin in CN104725781A is prepared by pre-polymerizing an amine modifier and bismaleimide in an organic solvent. The amine substance is an epoxy resin curing agent, after the amine reacts with the epoxy resin, the epoxy resin is subjected to ring opening to generate a large amount of hydroxyl, and the hydroxyl can reduce the ring opening temperature of the benzoxazine resin and accelerate the ring opening reaction of the benzoxazine, so that a large amount of hydroxyl and amino are rapidly generated in the system, the curing reaction of the whole system is accelerated, and the rheological window is narrowed.
Therefore, it is apparent that the development of a resin composition, and a prepreg and a laminate using the same, which have excellent heat resistance, strength, rigidity and flexibility, dielectric properties, low water absorption rate, and high glass transition temperature, and which do not cause dry streaks and white streaks in the sub-surface appearance of a copper clad laminate substrate, has positive practical significance.
Disclosure of Invention
The invention aims to provide a resin composition, and a prepreg, a metal foil laminated plate and an interlayer insulating film which are manufactured by using the resin composition.
In order to achieve the purpose of the invention, the technical scheme adopted by the invention is as follows: a resin composition comprising, based on 100 parts by weight of solids:
(a) diamine modified bismaleimide resin containing a benzoxazine structure: 40-80 parts;
(b) epoxy resin: 10-50 parts;
(c) polyphenylene ether: 10-40 parts;
the preparation method of the component (a) is as follows:
dissolving bismaleimide resin and diamine containing benzoxazine structure in an organic solvent, and reacting at 60-89 ℃ for 1-24 hr;
the mass ratio of the bismaleimide resin to diamine containing benzoxazine structure is 100: 30-30: 100, respectively;
the chemical formula of the diamine compound containing the benzoxazine structure is as follows:
wherein R is selected from-C (CH)3)2-、-SO2-or-CH2-，n＝2～4。
The mass ratio of the bismaleimide resin to diamine containing benzoxazine structure is 100: 30-30: 100, for example, the mass ratio of the bismaleimide resin to the diamine containing a benzoxazine structure is 100: 30. 100, and (2) a step of: 40. 100, and (2) a step of: 50. 100, and (2) a step of: 60. 100, and (2) a step of: 70. 100, and (2) a step of: 80. 100, and (2) a step of: 90. 100, and (2) a step of: 100. 90: 30. 90: 40. 90: 50. 90: 60. 90: 70. 90: 80. 90: 90. 90: 100. 80: 30. 80: 40. 80: 50. 80: 60. 80: 70. 80: 80. 80: 90. 80: 100. 70: 30. 70: 40. 70: 50. 70: 60. 70: 70. 70: 80. 70: 90. 70: 100. 60: 30. 60: 40. 60: 50. 60: 60. 60: 70. 60: 80. 60: 90. 60: 100. 50: 30. 50: 40. 50: 50. 50: 60. 50: 70. 50: 80. 50: 90. 50: 100. 40: 30. 40: 40. 40: 50. 40: 60. 40: 70. 40: 80. 40: 90. 40: 100. 30: 30. 30: 40. 30: 50. 30: 60. 30: 70. 30: 80. 30: 90. 30: 100, etc.
Preferably, the solid content of the diamine modified bismaleimide resin containing the benzoxazine structure is 30-90%. Preferably 50 to 80%. The solids content may typically, but not by way of limitation, be 40%, 60%, 70%, 85%, etc.
Preferably, the mass ratio of the bismaleimide resin to the diamine containing a benzoxazine structure is 60: 30-30: 60.
preferably, the paint comprises the following components in 100 parts by weight of solid:
(a) diamine modified bismaleimide resin containing a benzoxazine structure: 40-70 parts of a binder;
(b) epoxy resin: 10-30 parts;
(c) polyphenylene ether: 20-30 parts.
More preferably, component (a), component (b) and component (c) add up to 100 parts by weight solids and comprise:
(a) diamine modified bismaleimide resin containing a benzoxazine structure: 40-70 parts of a binder;
(b) epoxy resin: 10-30 parts;
(c) polyphenylene ether: 20-30 parts of a solvent;
(d) inorganic filler: 0-100 parts;
(e) flame retardant: 5-30 parts of a solvent;
(f) curing accelerator: 0.001 to 1 portion.
The flame retardant may be one or a mixture of more than two of common copper-clad plate flame retardants such as bromine-containing flame retardants, phosphorus-containing flame retardants or nitrogen-containing flame retardants.
The bromine-containing flame retardant is selected from at least one of decabromodiphenyl ether, decabromodiphenylethane, octabromodiphenyl ether, pentabromotoluene, hexabromocyclododecane, ethylene bis-tetrabromophthalimide, brominated polycarbonate, brominated polystyrene, brominated triazine, ethylene bis-pentabromobenzene, ethylene bis-tetrabromo imide, tetradecyl-bromophenoxy benzene, bis (tribromophenoxy) ethane, tetrabromobisphenol A and bromine-containing epoxy resin; the phosphorus-containing flame retardant is selected from tris (2, 6-dimethylphenyl) phosphine, 10- (2, 5-dihydroxyphenyl) -9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 2, 6-bis (2, 6-dimethylphenyl) phosphinobenzene or 10-phenyl-910-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, phosphazene, phosphorus-containing phenolic resin, phosphorus-containing epoxy resin, phenoxyphosphazene compound, phosphate ester, melamine polyphosphate, aluminum metaphosphate, triphenyl phosphate, bisphenol biphenyl phosphate, ammonium polyphosphate, phosphorus nitrogen-based compound, phosphorus nitrogen-coupled compound, bisphenol A bis (diphenyl phosphate), tris (2, 6-dimethylphenyl) phosphine, resorcinol bis [ bis (2, 6-dimethylphenyl) phosphate ]; the nitrogen-containing flame retardant is selected from one of triazine compounds, cyanuric acid compounds, isocyanic acid compounds and phenothiazine, and the content of the nitrogen-containing flame retardant is preferably 10-20 parts.
In the above technical solution, the inorganic filler is at least one selected from the group consisting of silica (molten or non-molten and porous), alumina, magnesia, magnesium hydroxide, calcium carbonate, aluminum nitride, boron nitride, aluminum hydroxide, aluminum silicon carbide, sodium carbonate, titanium dioxide, zinc oxide, zirconia, quartz, diamond powder, diamond-like powder, glass powder, graphite, magnesium carbonate, potassium titanate, ceramic fiber, mica, boehmite, zinc molybdate, ammonium molybdate, zinc borate, calcium phosphate, calcium silicate, calcium carbonate, calcined talc, silicon nitride, calcined kaolin, clay, magnesium sulfate, barium sulfate, strontium titanate, and barium titanate, and the content thereof is preferably 10 to 80 parts.
The shape of the inorganic filler is not particularly limited, and may be spherical, plate-like, needle-like, angular, amorphous, or a mixture thereof. The inorganic filler may be surface-treated with a silane coupling agent to improve dispersibility in the resin composition. When used, the inorganic filler may be directly added to the resin composition, or a filler dispersion may be prepared in advance, or a paste may be added to the resin composition.
In the technical scheme, the curing accelerator is selected from imidazoles, pyridines, triphenylphosphine, boron trifluoride monoethylamine and carboxylic acid metal salts. The imidazoles are selected from 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-undecylimidazole and 1-cyanoethyl substituted imidazole; the pyridine is selected from triethylamine, benzyl dimethylamine or dimethylamino pyridine; the metal carboxylate is metal acetylacetonate, metal octanoate, metal isooctanoate or metal naphthenate, and the metal is selected from zinc, cobalt, copper, manganese, iron, nickel, aluminum and a mixture thereof.
The above-mentioned technical means may further include an epoxy resin curing agent, which may be an amide-based compound, an acid anhydride-based compound, a phenol-based compound, or the like, but does not include an amine-based curing agent. The amide compound may be dicyandiamide, low molecular polyamide, or the like; the acid anhydride compound may be phthalic anhydride, trimellitic anhydride, pyromellitic dianhydride, maleic anhydride, hydrogenated phthalic anhydride, nadic anhydride, or the like; the phenolic compound may be a phosphorus-containing phenolic resin, a nitrogen-containing phenolic resin, a bisphenol a phenolic resin, a phenol phenolic resin, a naphthol phenolic resin, a biphenyl-modified naphthol resin, a dicyclopentadiene phenol addition-type resin, a phenol aralkyl resin, a naphthol aralkyl resin, a trimethylolmethane resin, a benzoxazine resin, or the like, and the content thereof is 1 to 80 parts based on 100 parts of the epoxy resin.
Preferably, the chemical formula of the bismaleimide resin is as follows:
wherein,
r1 is selected from:r2 and R3 are the same or different and are respectively selected from H and H3C-or C2H5-。
In the above technical solution, the bismaleimide resin is preferably one or a mixture of more than one of 4,4 ' -diphenylmethane bismaleimide, 4 ' -diphenyl ether bismaleimide, 4 ' -diphenylsulfone bismaleimide and bis (3-ethyl-5-methyl-4-maleimidobenzene) methane.
Preferably, the epoxy resin is selected from one or more of isocyanate modified bisphenol a epoxy resin, isocyanate modified bisphenol F epoxy resin, isocyanate modified bisphenol S epoxy resin, phenol novolac epoxy resin, bisphenol a epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, o-cresol novolac epoxy resin, trifunctional epoxy resin, tetrafunctional epoxy resin, dicyclopentadiene epoxy resin, p-aminophenol epoxy resin, cyanuric acid epoxy resin, phosphorus-containing epoxy resin, nitrogen-containing epoxy resin, bromine-containing epoxy resin, p-xylene epoxy resin, naphthalene epoxy resin, benzopyran epoxy resin, diphenol novolac epoxy resin and phenol-based phenylalkyl phenol novolac epoxy resin.
In the technical scheme, the polyphenyl ether is epoxy modified polyphenyl ether, carbon-carbon unsaturated double bond modified polyphenyl ether, phenol modified polyphenyl ether or a composition thereof, and the number average molecular weight of the polyphenyl ether is 500-5000 g/mol.
Preferably, the bismaleimide resin and the diamine containing the benzoxazine structure are dissolved in an organic solvent and react for 1-24 hours at the temperature of 60-89 ℃. Wherein the reaction temperature is typically, but not limited to, 61 ℃, 62 ℃, 63 ℃, 64 ℃, 65 ℃, 66 ℃, 67 ℃, 68 ℃, 69 ℃, 70 ℃, 71 ℃, 72 ℃, 73 ℃, 74 ℃, 75 ℃, 76 ℃, 77 ℃, 78 ℃, 79 ℃, 80 ℃, 81 ℃, 82 ℃, 83 ℃, 84 ℃, 85 ℃, 86 ℃, 87 ℃, 89 ℃ and the like. The preferable reaction temperature is 70-80 ℃.
Wherein the reaction time is typically, but not limited to, 2hr, 3hr, 4hr, 5hr, 6hr, 7hr, 8hr, 9hr, 10hr, 12hr, 14hr, 16hr, 18hr, 20hr, 21hr, 22hr, 23hr, etc.
Preferably, the bismaleimide resin and the diamine containing the benzoxazine structure are dissolved in an organic solvent and react for 2-10 hr at the temperature of 70-80 ℃.
The organic solvent is selected from one or more of acetone, butanone, toluene, xylene, methanol, ethanol, methyl isobutyl ketone, cyclohexanone, methyl ethyl ketone, N, N-dimethylformamide, N, N-dimethylacetamide, ethylene glycol methyl ether, propylene glycol methyl ether, methoxyethyl acetate, ethoxyethyl acetate, propoxyethyl acetate and ethyl acetate.
The working principle of the invention is as follows: the diamine containing benzoxazine structure and bismaleimide resin are preferentially reacted in a solvent at the temperature of below 90 ℃ (excluding 90 ℃) to form a prepolymer, when the reaction temperature is below 90 ℃ (excluding 90 ℃), the reaction between terminal amino and bismaleimide in the resin is mainly carried out, and the benzoxazine hardly has ring opening; in addition, in the invention, a part of reaction groups are consumed through pre-reaction to form a prepolymer with a certain molecular weight, so that the steric hindrance of the benzoxazine ring-opening reaction is increased, the reaction rate of the benzoxazine structure in the resin structure is slowed down, the rheological window in the pressing process is widened, and the risk of drying or white lines of the copper-clad plate substrate is greatly reduced.
The invention simultaneously requests to protect a prepreg made of the resin composition, the resin composition is dissolved by a solvent to prepare a glue solution, and then a reinforcing material is soaked in the glue solution; and heating and drying the impregnated reinforcing material to obtain the prepreg.
The solvent is at least one selected from acetone, butanone, toluene, xylene, methanol, ethanol, methyl isobutyl ketone, cyclohexanone, methyl ethyl ketone, N, N-dimethylformamide, N, N-dimethylacetamide, ethylene glycol methyl ether, propylene glycol methyl ether, methoxyethyl acetate, ethoxyethyl acetate, propoxyethyl acetate and ethyl acetate.
In the above technical solution, the reinforcing material is glass fiber cloth, such as D glass, E glass, NE glass, S glass, and T glass. The thickness of the glass fiber cloth is not particularly limited, but for producing a laminate having a thickness of 0.01 to 0.02mm, a spread cloth or a flat cloth is generally used. In addition, in order to improve the interfacial bonding between the resin and the glass cloth, the glass cloth generally needs to be chemically treated, mainly by a coupling agent such as epoxy silane and amino silane.
The invention also relates to a laminate comprising at least one prepreg as described above.
The invention also discloses a metal foil laminated board, wherein a metal foil is coated on one side or both sides of one prepreg, or at least 2 prepregs are stacked, then the metal foil is coated on one side or both sides of the prepreg, and hot press forming is carried out, so that the metal foil laminated board can be obtained.
The number of prepregs is determined according to the thickness of the metal foil laminate required by a customer, and one or more prepregs can be used. The metal foil may be a copper foil or an aluminum foil, and the thickness thereof is not particularly limited.
The invention also requests to protect a printed circuit board, which comprises at least one prepreg;
or at least one laminate as described above;
or at least one metal foil laminate as described above.
The invention also discloses an interlayer insulating film prepared from the resin composition, a solvent is added into the resin composition to be dissolved to prepare a glue solution, the glue solution is coated on a carrier film, the carrier film coated with the glue solution is heated and dried to obtain the interlayer insulating film, and the heating and drying conditions are that the interlayer insulating film is baked at 50-170 ℃ for 1-10 minutes.
In the above technical solution, the solvent is at least one selected from acetone, butanone, toluene, xylene, methanol, ethanol, methyl isobutyl ketone, cyclohexanone, methyl ethyl ketone, N, N-dimethylformamide, N, N-dimethylacetamide, ethylene glycol methyl ether, propylene glycol methyl ether, methoxyethyl acetate, ethoxyethyl acetate, propoxyethyl acetate, and ethyl acetate.
In the above technical solution, the carrier film may be a polyethylene terephthalate (PET) film, a release film, a copper foil, an aluminum foil, or the like, and the carrier film is preferably a PET film.
In the above technical solution, in order to protect the insulating resin layer, the other surface of the resin layer is covered with a protective film, and the protective film may be made of the same material as the carrier film.
Due to the application of the technical scheme, compared with the prior art, the invention has the following advantages:
1. the modified bismaleimide resin of the invention is prepared by the preferential pre-reaction of bismaleimide and diamine resin containing benzoxazine at low temperature (below 90 ℃ and excluding 90 ℃), and the benzoxazine hardly has ring opening at low temperature (below 90 ℃ and excluding 90 ℃); in addition, a part of reaction groups are consumed through pre-reaction, a prepolymer with a certain molecular weight is formed, the steric hindrance of the benzoxazine ring-opening reaction is increased, the reaction rate of the benzoxazine structure in the resin structure in a system is slowed down, the rheological reaction window of the resin composition is well adjusted (the rheological window in a rheological curve graph is widened), and the risk that the substrate is dry or white due to the over-quick reaction of the resin composition in the pressing process is reduced; experiments show that the invention can not form dry flowers and white lines on the secondary appearance of the copper-clad plate base material, and obtains remarkable effect;
2. experiments show that the modified bismaleimide resin disclosed by the invention not only maintains better heat resistance and rigidity, reduces the curing reaction temperature and water absorption rate, is more favorable for application in the field of copper-clad plates, ensures application in the fields of aerospace and thinned copper-clad plates due to high heat resistance and rigidity, reduces the expansion and shrinkage proportion of a base material after absorbing water due to low water absorption rate, and inhibits the generation of plate warpage;
3. the modified bismaleimide resin with high glass transition temperature, good heat resistance and low water absorption is adopted, the diamine resin containing benzoxazine structure is used for modifying the bismaleimide resin, the modified resin has good solubility, and the cured product has high glass transition temperature and low water absorption, so that the problem of high water absorption of the bismaleimide resin in the prior art is solved, the warpage rate of a plate is greatly reduced, and a great problem is solved for the application of the bismaleimide resin in the fields of aerospace and electronics;
4. the diamine modified bismaleimide resin, epoxy resin and polyphenyl ether resin composition containing the benzoxazine structure has good compatibility, and the prepared copper-clad plate has good heat resistance, high glass transition temperature, low water absorption, low warping degree, low dielectric constant, dielectric loss tangent value and good rigidity, and can well meet the requirements of rigidity and warping degree of a thin substrate in the processes of impedance design and printed circuit processing.
Drawings
Fig. 1 is a rheological graph of prepregs in examples of the present invention and comparative examples.
Detailed Description
The invention is further described below with reference to the following examples:
the following is a specific embodiment of the preparation of diamine modified bismaleimide resin containing benzoxazine to obtain modified resin:
synthesis example 1
In a 500ml three-necked flask equipped with a stirrer, a reflux condenser and a thermometer, placed in an oil bath, bisphenol A: 91.2g, p-phenylenediamine: 94.4g, formaldehyde: 48.0 g; adding 80ml ethanol and 20ml toluene as solvent, slowly heating to 75 deg.C and maintaining for 3hr while continuously stirring, and introducing nitrogen into three-neck flask for bubbling protection. And (3) after the reaction is finished, cooling the product to room temperature, maintaining stirring, dropwise adding a methanol solution into the flask until no precipitate is separated out, stopping stirring, standing at room temperature for 24 hours, filtering to remove a supernatant, collecting the precipitate, placing the precipitate in a vacuum drying oven at 50 ℃, and drying for 5 hours to obtain diamine containing a benzoxazine structure, which is recorded as N (BOZ) -1.
Synthesis example II
In a 500ml three-necked flask equipped with a stirrer, a reflux condenser and a thermometer, placed in an oil bath, bisphenol F: 79.2g, p-phenylenediamine: 94.4g, formaldehyde: 48.0 g; adding 80ml ethanol and 20ml toluene as solvent, slowly heating to 60 deg.C and maintaining for 5hr while continuously stirring, and introducing nitrogen into three-neck flask for bubbling protection. And (3) after the reaction is finished, cooling the product to room temperature, maintaining stirring, dropwise adding a methanol solution into the flask until no precipitate is separated out, stopping stirring, standing at room temperature for 24 hours, filtering to remove a supernatant, collecting the precipitate, placing the precipitate in a vacuum drying oven at 50 ℃, and drying for 5 hours to obtain diamine containing a benzoxazine structure, which is recorded as N (BOZ) -2.
Example of modified resin
Adding 100g of solvent N, N-dimethylformamide into a 500ml three-neck flask, adding 4, 4' -diphenylmethane bismaleimide and diamine resin N (BOZ) -1 containing benzoxazine structure into the three-neck flask in sequence according to the mass part of 100g:30g, continuously stirring under the condition of an oil bath at 75 ℃, starting timing after the solid in the flask is completely dissolved, and continuously stirring for 2.5 hours, and distilling the obtained product to obtain a modified bismaleimide resin solution 1 with the solid content of 75%.
Modified resin example II
Adding 120g of solvent N, N-dimethylacetamide into a 500ml three-neck flask, adding 4, 4' -diphenylmethane bismaleimide and diamine resin N (BOZ) -1 containing benzoxazine structure into the three-neck flask in sequence according to the mass portion of 100g:50g, continuously stirring under the condition of oil bath at 85 ℃, timing when the solid in the flask is completely dissolved, continuously stirring for 1hr, and distilling the obtained product to obtain a modified bismaleimide resin solution 2 with the solid content of 60%.
Modified resin example III
150g of acetone solvent is added into a 500ml three-neck flask, bis (3-ethyl-5-methyl-4-maleimide benzene) methane and diamine resin N (BOZ) -2 containing benzoxazine structure are put into the three-neck flask according to the mass portion of 100g:100g in sequence, the mixture is continuously stirred under the condition of oil bath at 70 ℃, the time is counted after the solid in the flask is completely dissolved, the continuous stirring is carried out for 8 hours, and the obtained product is distilled, so that the modified bismaleimide resin solution 3 with the solid content of 60% is obtained.
Example four of modified resin
Adding 100g of solvent N, N-dimethylacetamide into a 500ml three-neck flask, adding 4, 4' -diphenyl ether bismaleimide and diamine resin N (BOZ) -2 containing benzoxazine structure into the three-neck flask in sequence according to the mass portion of 30g:100g, continuously stirring under the condition of an oil bath at 80 ℃, timing when the solid in the flask is completely dissolved, continuously stirring for 4 hours, and distilling the obtained product to obtain a modified bismaleimide resin solution 4 with the solid content of 65%.
Modified resin example five
Adding 100g of solvent N, N-dimethylformamide into a 500ml three-neck flask, adding 4, 4' -diphenylmethane bismaleimide and diamine resin N (BOZ) -1 containing benzoxazine structure into the three-neck flask in sequence according to the mass part of 100g:30g, continuously stirring under the condition of an oil bath at 60 ℃, timing when the solid in the flask is completely dissolved, continuously stirring for 2.5 hours, and distilling the obtained product to obtain a modified bismaleimide resin solution 5 with the solid content of 75%.
Comparative example of modified resin 1
Placing 4, 4' -diphenylmethane bismaleimide and diallyl bisphenol A resin in a mass ratio of 100:60 into a flask, and reacting for 100min under the condition of 130 ℃ oil bath to obtain the allyl modified bismaleimide 1.
Comparative example of modified resin
Weighing 100g of 4, 4' -diphenylmethane bismaleimide and 40g of diaminodiphenylmethane, dissolving in DMF solution, and reacting at 100 ℃ for 5hr to obtain amine modified bismaleimide 2.
Comparative example No. III of modified resin
Adding 100g of solvent N, N-dimethylacetamide into a 500ml three-neck flask, adding 4, 4' -diphenyl ether bismaleimide and diamine resin N (BOZ) -2 containing benzoxazine structure into the three-neck flask in sequence according to the mass portion of 30g:100g, continuously stirring under the condition of an oil bath at 50 ℃, timing when the solid in the flask is completely dissolved, continuously stirring for 4 hours, and distilling the obtained product to obtain a modified bismaleimide resin solution 6 with the solid content of 65%.
Comparative example No. four modified resin
Adding 100g of solvent N, N-dimethylformamide into a 500ml three-neck flask, adding 4, 4' -diphenylmethane bismaleimide and diamine resin N (BOZ) -1 containing benzoxazine structure into the three-neck flask in sequence according to the mass part of 100g:30g, continuously stirring under the condition of an oil bath at 100 ℃, timing when the solid in the flask is completely dissolved, continuously stirring for 2.5 hours, and distilling the obtained product to obtain a modified bismaleimide resin solution 7 with the solid content of 75%.
Preparation of prepreg and copper-clad plate
Weighing the diamine modified bismaleimide resin containing benzoxazine prepared in the resin modification example according to the data in the table 1 according to the solid mass, adding epoxy resin, inorganic filler and a curing accelerator, adjusting the solid content of the glue solution to 60% through a solvent, coating the glue solution on glass fiber cloth, soaking for a moment, baking for 3-6 min in a 160 ℃ blast drying oven to prepare a prepreg, cutting the prepreg to a certain size, placing an electrolytic copper foil on the upper side and the lower side respectively, overlapping to form a certain overlapping structure, sending the overlapping structure into a vacuum press for pressing, wherein the program is 150 ℃/60min +200 ℃/120min, and preparing the metal foil laminated board, and the specific performance detection is shown in the table 3.
TABLE 1 resin composition content data
TABLE 2 materials and manufacturers
| Name (R) | Manufacturer of the product |
| Bis (3-ethyl-5-methyl-4-maleimide-phenyl) methane | New material of Xian Shuangma |
| 4, 4' -diphenylmethane bismaleimide | New material of Xian Shuangma |
| 4, 4' -Diphenylisopropylbismaleimide | New material of Xian Shuangma |
| Epoxy resin 1 (bisphenol A type epoxy resin) | Dow |
| Epoxy resin 2 (naphthalene ring type epoxy resin) | Dic |
| Polyphenylene ether 1 (epoxy modified) | Asahi Kasei |
| Polyphenylene ether 2 (carbon-carbon unsaturated group modified) | Asahi Kasei |
| Bisphenol A benzoxazine resin | Huntsman |
| Flame retardant 1 (phosphorus-containing phenolic resin) | Dow |
| Flame retardant 2 (decabromodiphenyl ether) | Yabao (elegant treasure) |
| Filler (silicon dioxide) | Jiangsu alli |
| Curing accelerator (2-methylimidazole) | Formation of four countries |
And (3) carrying out performance test on the prepregs and the copper-clad plates prepared in all the examples and the comparative examples. The test method comprises the following steps:
glass transition Temperature (TMA): testing Tg of the plate by using a relaxation-resistant TMA instrument, wherein the heating rate is as follows: 10 ℃/min, temperature range: 30-320 ℃.
Glass transition temperature (DMA): the Tg of the plate was measured using a TA DMA Q800 instrument, the rate of temperature rise: 3 ℃/min, temperature range: 30-320 ℃.
Peel Strength (PS): the peel strength of the metal cap was tested according to the "post thermal stress" experimental conditions in the IPC-TM-650 method.
Tin immersion heat resistance: A50X 50mm sample with copper on both sides was immersed in solder at 288 ℃ and the time to delamination blistering of the sample was recorded.
Tin immersion heat resistance after moisture treatment: after 3 pieces of 100X 100mm substrate samples were held in a pressure cooker at 121 ℃ and 105Kpa for 3 hours, the samples were immersed in a solder bath at 288 ℃ for 2 minutes to observe whether or not delamination bubbling occurred in the samples, wherein 3 pieces of samples were designated as 3/3, 2 pieces of samples were designated as 2/3, 1 piece of samples were designated as 1/3, and 0 piece of samples were designated as 0/3.
D23 ℃/24hr water absorption: the measurement was carried out according to the standard method specified in IPC-TM-650
D23 ℃/24hr post-imbibition collapsible: and (3) adopting a triaxial coordinate method to test the expansion and contraction condition of the substrate after water absorption, wherein the expansion of the base material is represented by a plus value, and the contraction of the base material is represented by a minus value, and the unit is ppm, namely one part per million.
The warping degree of the plate is as follows: and testing by adopting a standard method specified in IPC-TM-650 to obtain the maximum percent of bow and the maximum percent of distortion so as to judge the warping degree of the copper-clad plate base material.
Bending strength: the standard method specified in IPC-TM-650.
Dielectric properties: the dielectric constant and the dielectric loss tangent at 1GHz were measured by the plate method according to IPC-TM-6502.5.5.9.
The secondary appearance of the substrate: the standard method specified in IPC-TM-650 is adopted for testing, and whether the defects such as dry flowers, white lines and the like exist in the base material is judged by visual inspection or a slicing method.
Prepreg powder rheology test: the rheological curve of the sample is tested by adopting an Antopa MCR302 rheometer, and the temperature range is as follows: 80-160 ℃, heating rate: 3 ℃/min.
TABLE 3 copper clad laminate base Performance data for examples and comparative examples
The [ scatter ] wrongly written problem in tables is proactive modification.
As can be seen from the above examples and comparative examples, the use of the diamine-modified bismaleimide resin containing benzoxazine, the composition of epoxy resin and polyphenylene ether resin (example 1) obtained lower water absorption and warpage than the use of allyl compound (comparative example 1) or ordinary diamine-modified bismaleimide resin (comparative example 2), the composition of epoxy resin and polyphenylene ether resin, and maintained high glass transition temperature and excellent wet heat resistance, and comparative examples 1 and 2 failed to prepare copper clad laminates due to glue phase separation.
Furthermore, the composition formed by pre-polymerizing the diamine containing benzoxazine and bismaleimide resin and forming the epoxy resin and polyphenylene oxide resin (example 2) has lower water absorption and dimensional expansion and contraction, wider rheological window compared with the composition formed by the conventional diamine modified bismaleimide resin, polyphenylene oxide, benzoxazine resin and epoxy resin (comparative example 5), is more beneficial to process control in the lamination process of the laminated board, reduces the risk of dry and white stripes appearing on the secondary appearance of the substrate and is more beneficial to the manufacture of the copper-clad plate.
Furthermore, the pre-polymerization of benzoxazine-containing diamines with bismaleimide resins at temperatures below 90 ℃ (example 1) has a broader rheological window (see broadening of the rheological window in the rheological profile of fig. 1) compared to pre-polymerization at temperatures above 90 ℃ (comparative example 7), while significantly improving the substrate sub-apparent quality; the technical proposal of pre-polymerizing the diamine containing benzoxazine and bismaleimide resin at the temperature of 60 ℃ (comparative example 6) makes it difficult to prepare the copper-clad plate due to phase separation of glue solution.
Furthermore, the overall performance of example 1 (prepolymerization at a temperature of 75 ℃) is better than that of example 5 (prepolymerization at a temperature of 60 ℃).
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. A resin composition characterized by comprising, based on solid weight, component (a), component (b) and component (c) in total 100 parts:
(a) diamine modified bismaleimide resin containing a benzoxazine structure: 40-80 parts;
(b) epoxy resin: 10-50 parts;
(c) polyphenylene ether: 10-40 parts;
the preparation method of the component (a) is as follows:
dissolving bismaleimide resin and diamine containing benzoxazine structure in an organic solvent, and reacting at 60-89 ℃ for 1-24 hr;
the mass ratio of the bismaleimide resin to diamine containing benzoxazine structure is 100: 30-30: 100, respectively;
the chemical formula of the diamine compound containing the benzoxazine structure is as follows:
wherein R is selected from-C (CH)3)2-、-SO2-or-CH2-，n＝2～4。
2. The resin composition according to claim 1, characterized in that: the component (a), the component (b) and the component (c) are 100 parts by weight, and comprise:
(a) diamine modified bismaleimide resin containing a benzoxazine structure: 40-70 parts of a binder;
(b) epoxy resin: 10-30 parts;
(c) polyphenylene ether: 20-30 parts.
3. The resin composition according to claim 1, characterized in that: the component (a), the component (b) and the component (c) are 100 parts by weight, and comprise:
(a) diamine modified bismaleimide resin containing a benzoxazine structure: 40-70 parts of a binder;
(b) epoxy resin: 10-30 parts;
(c) polyphenylene ether: 20-30 parts of a solvent;
(d) inorganic filler: 0-100 parts;
(e) flame retardant: 5-30 parts of a solvent;
(f) curing accelerator: 0.001 to 1 portion.
4. The resin composition according to claim 1, 2 or 3, characterized in that: the chemical formula of the bismaleimide resin is as follows:
wherein R is1Selected from:R2and R3Same or different, are respectively selected from H and H3C-or C2H5-。
5. The resin composition according to claim 1, 2 or 3, characterized in that: the polyphenyl ether is epoxy modified polyphenyl ether, carbon-carbon unsaturated double bond modified polyphenyl ether, phenol modified polyphenyl ether or a composition thereof, and the number average molecular weight of the polyphenyl ether is 500-5000 g/mol.
6. The resin composition according to claim 1, 2 or 3, characterized in that: dissolving bismaleimide resin and diamine containing benzoxazine structure in an organic solvent, and reacting at 70-80 ℃ for 2-10 hr.
7. A prepreg produced using the resin composition according to claim 1, 2 or 3, characterized in that: dissolving the resin composition of claim 1, 2 or 3 with a solvent to form a glue solution, and then impregnating a reinforcing material in the glue solution; and heating and drying the impregnated reinforcing material to obtain the prepreg.
8. A laminate, characterized by: comprising at least one prepreg according to claim 7.
9. A metal foil laminate characterized by: coating a metal foil on one side or both sides of a prepreg according to claim 7, or coating a metal foil on one side or both sides of at least 2 prepregs according to claim 7 after laminating the prepregs, and hot-press forming to obtain the metal foil laminate.
10. An interlayer insulating film characterized in that: the resin composition according to claim 1, 2 or 3 is coated on a carrier film, and the interlayer insulating film is obtained by heating and drying the carrier film coated with the resin composition.
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| CN111117154B (en) * | 2019-12-31 | 2022-10-18 | 广东生益科技股份有限公司 | Flame-retardant thermosetting resin composition, and prepreg, laminated board and printed circuit board manufactured from same |
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| CN103030933A (en) * | 2012-11-23 | 2013-04-10 | 中国航空工业集团公司北京航空材料研究院 | Method for reducing cure shrinkage rate of resin matrix for liquid molding |
| CN104725781B (en) * | 2015-03-11 | 2017-11-03 | 广东生益科技股份有限公司 | A kind of resin combination and use its prepreg and laminate |
| CN106046786A (en) * | 2016-08-22 | 2016-10-26 | 威海光威复合材料股份有限公司 | Method for preparing composite material from nanometer ceramic powder modified bismaleimide resin |
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