CN115073907B - Resin composition, compound, prepreg, electric copper-clad plate and preparation method and application thereof - Google Patents
Resin composition, compound, prepreg, electric copper-clad plate and preparation method and application thereof Download PDFInfo
- Publication number
- CN115073907B CN115073907B CN202210732169.0A CN202210732169A CN115073907B CN 115073907 B CN115073907 B CN 115073907B CN 202210732169 A CN202210732169 A CN 202210732169A CN 115073907 B CN115073907 B CN 115073907B
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- China
- Prior art keywords
- resin composition
- prepreg
- compound
- bvpe
- resin
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- 239000011342 resin composition Substances 0.000 title claims abstract description 137
- 150000001875 compounds Chemical class 0.000 title claims abstract description 123
- 238000002360 preparation method Methods 0.000 title claims abstract description 44
- 229920005989 resin Polymers 0.000 claims abstract description 58
- 239000011347 resin Substances 0.000 claims abstract description 58
- 239000003999 initiator Substances 0.000 claims abstract description 32
- 229920013636 polyphenyl ether polymer Polymers 0.000 claims abstract description 17
- 229920000642 polymer Polymers 0.000 claims abstract description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 46
- 238000000034 method Methods 0.000 claims description 39
- CMLFRMDBDNHMRA-UHFFFAOYSA-N 2h-1,2-benzoxazine Chemical compound C1=CC=C2C=CNOC2=C1 CMLFRMDBDNHMRA-UHFFFAOYSA-N 0.000 claims description 36
- -1 methylene, isopropyl Chemical group 0.000 claims description 35
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 34
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 31
- 239000000126 substance Substances 0.000 claims description 30
- 239000012779 reinforcing material Substances 0.000 claims description 27
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 26
- 238000003825 pressing Methods 0.000 claims description 20
- 239000002904 solvent Substances 0.000 claims description 20
- 125000000217 alkyl group Chemical group 0.000 claims description 19
- 125000004432 carbon atom Chemical group C* 0.000 claims description 18
- 239000011889 copper foil Substances 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 18
- 239000000377 silicon dioxide Substances 0.000 claims description 17
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 14
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical group O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 13
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 13
- 239000000945 filler Substances 0.000 claims description 13
- 238000003475 lamination Methods 0.000 claims description 13
- 239000004744 fabric Substances 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 12
- 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 11
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 11
- 235000012239 silicon dioxide Nutrition 0.000 claims description 11
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 10
- 239000004593 Epoxy Substances 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 10
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 10
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 10
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 10
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 10
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 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 9
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 9
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 9
- 229920002554 vinyl polymer Polymers 0.000 claims description 9
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-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
- 239000008096 xylene Substances 0.000 claims description 7
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 claims description 6
- 239000012766 organic filler Substances 0.000 claims description 6
- 150000002978 peroxides Chemical class 0.000 claims description 6
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 claims description 6
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 5
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims description 5
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 claims description 4
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims description 4
- 238000010526 radical polymerization reaction Methods 0.000 claims description 4
- CUZLJOLBIRPEFB-UHFFFAOYSA-N 1-methoxypropan-2-one Chemical compound COCC(C)=O CUZLJOLBIRPEFB-UHFFFAOYSA-N 0.000 claims description 3
- FPZWZCWUIYYYBU-UHFFFAOYSA-N 2-(2-ethoxyethoxy)ethyl acetate Chemical compound CCOCCOCCOC(C)=O FPZWZCWUIYYYBU-UHFFFAOYSA-N 0.000 claims description 3
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 claims description 3
- 229910052582 BN Inorganic materials 0.000 claims description 3
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 3
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 3
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 3
- 239000004734 Polyphenylene sulfide Substances 0.000 claims description 3
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 3
- DWSWCPPGLRSPIT-UHFFFAOYSA-N benzo[c][2,1]benzoxaphosphinin-6-ium 6-oxide Chemical compound C1=CC=C2[P+](=O)OC3=CC=CC=C3C2=C1 DWSWCPPGLRSPIT-UHFFFAOYSA-N 0.000 claims description 3
- 239000000835 fiber Substances 0.000 claims description 3
- 230000000977 initiatory effect Effects 0.000 claims description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 3
- 238000012986 modification Methods 0.000 claims description 3
- 230000004048 modification Effects 0.000 claims description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 3
- 229920000069 polyphenylene sulfide Polymers 0.000 claims description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 claims description 3
- 239000011265 semifinished product Substances 0.000 claims description 3
- 229920002994 synthetic fiber Polymers 0.000 claims description 3
- 239000012209 synthetic fiber Substances 0.000 claims description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims 1
- 150000005130 benzoxazines Chemical class 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 229910052698 phosphorus Inorganic materials 0.000 claims 1
- 239000011574 phosphorus Substances 0.000 claims 1
- 239000002861 polymer material Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 23
- PJANXHGTPQOBST-VAWYXSNFSA-N Stilbene Natural products C=1C=CC=CC=1/C=C/C1=CC=CC=C1 PJANXHGTPQOBST-VAWYXSNFSA-N 0.000 description 18
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 18
- 235000021286 stilbenes Nutrition 0.000 description 18
- 229920001955 polyphenylene ether Polymers 0.000 description 11
- 229940125904 compound 1 Drugs 0.000 description 10
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical class C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 10
- 229940126062 Compound A Drugs 0.000 description 9
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 9
- 229940125782 compound 2 Drugs 0.000 description 8
- 229910052802 copper Inorganic materials 0.000 description 8
- 239000010949 copper Substances 0.000 description 8
- 238000004132 cross linking Methods 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 150000003440 styrenes Chemical class 0.000 description 8
- 238000001816 cooling Methods 0.000 description 7
- 239000000178 monomer Substances 0.000 description 7
- 238000009472 formulation Methods 0.000 description 6
- 150000002430 hydrocarbons Chemical group 0.000 description 6
- 230000001976 improved effect Effects 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000013032 Hydrocarbon resin Substances 0.000 description 5
- 210000001072 colon Anatomy 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229920006270 hydrocarbon resin Polymers 0.000 description 5
- ABKRGXBSJGYCFA-UHFFFAOYSA-N 1-(2-phenylethenyl)-2-propan-2-ylbenzene Chemical compound CC(C)C1=CC=CC=C1C=CC1=CC=CC=C1 ABKRGXBSJGYCFA-UHFFFAOYSA-N 0.000 description 4
- GEUYACYJMUQXCF-UHFFFAOYSA-N 1-ethyl-2-(2-phenylethenyl)benzene Chemical compound CCC1=CC=CC=C1C=CC1=CC=CC=C1 GEUYACYJMUQXCF-UHFFFAOYSA-N 0.000 description 4
- PEBXLTUWFWEWGV-VAWYXSNFSA-N 1-methyl-2-[(e)-2-phenylethenyl]benzene Chemical compound CC1=CC=CC=C1\C=C\C1=CC=CC=C1 PEBXLTUWFWEWGV-VAWYXSNFSA-N 0.000 description 4
- MDRVHDXASYPUCB-VAWYXSNFSA-N 1-methyl-4-[(e)-2-phenylethenyl]benzene Chemical compound C1=CC(C)=CC=C1\C=C\C1=CC=CC=C1 MDRVHDXASYPUCB-VAWYXSNFSA-N 0.000 description 4
- 150000003923 2,5-pyrrolediones Chemical class 0.000 description 4
- CEBRPXLXYCFYGU-UHFFFAOYSA-N 3-methylbut-1-enylbenzene Chemical compound CC(C)C=CC1=CC=CC=C1 CEBRPXLXYCFYGU-UHFFFAOYSA-N 0.000 description 4
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- MPMBRWOOISTHJV-UHFFFAOYSA-N but-1-enylbenzene Chemical compound CCC=CC1=CC=CC=C1 MPMBRWOOISTHJV-UHFFFAOYSA-N 0.000 description 4
- 239000003365 glass fiber Substances 0.000 description 4
- 230000009477 glass transition Effects 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- RCALDWJXTVCBAZ-UHFFFAOYSA-N oct-1-enylbenzene Chemical compound CCCCCCC=CC1=CC=CC=C1 RCALDWJXTVCBAZ-UHFFFAOYSA-N 0.000 description 4
- KHMYONNPZWOTKW-UHFFFAOYSA-N pent-1-enylbenzene Chemical compound CCCC=CC1=CC=CC=C1 KHMYONNPZWOTKW-UHFFFAOYSA-N 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 238000005979 thermal decomposition reaction Methods 0.000 description 4
- 229930185605 Bisphenol Natural products 0.000 description 3
- 239000004721 Polyphenylene oxide Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000032798 delamination Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 229920006380 polyphenylene oxide Polymers 0.000 description 3
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- FPVSUJTZRASPAK-UHFFFAOYSA-N (2,3-dimethylbenzoyl) 2,3-dimethylbenzenecarboperoxoate Chemical compound CC1=CC=CC(C(=O)OOC(=O)C=2C(=C(C)C=CC=2)C)=C1C FPVSUJTZRASPAK-UHFFFAOYSA-N 0.000 description 2
- STDXPWQTVGDGKE-NELGMTEASA-N diethyldicyclopentadiene Chemical compound C([C@H]1C=C2CC)[C@H]2C2C1C=C(CC)C2 STDXPWQTVGDGKE-NELGMTEASA-N 0.000 description 2
- YOUYWVQGYBDAKE-UHFFFAOYSA-N formyloxy formate Chemical compound O=COOC=O YOUYWVQGYBDAKE-UHFFFAOYSA-N 0.000 description 2
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 2
- 150000003949 imides Chemical group 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- 229920003192 poly(bis maleimide) Polymers 0.000 description 2
- 150000003254 radicals Chemical group 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000008054 signal transmission Effects 0.000 description 2
- 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 description 1
- ZXLAFQNTMMFLSA-UHFFFAOYSA-N 1-ethenyl-4-[2-(4-ethenylphenyl)ethyl]benzene Chemical compound C1=CC(C=C)=CC=C1CCC1=CC=C(C=C)C=C1 ZXLAFQNTMMFLSA-UHFFFAOYSA-N 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000002355 alkine group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- WOFVLGVIZDWRHB-UHFFFAOYSA-N cyclohexane stilbene Chemical compound C1CCCCC1.C1(=CC=CC=C1)C=CC1=CC=CC=C1 WOFVLGVIZDWRHB-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 description 1
- NOMRCDXYHTWTNR-UHFFFAOYSA-N diphenylmethanediamine;pyrrole-2,5-dione Chemical compound O=C1NC(=O)C=C1.O=C1NC(=O)C=C1.C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 NOMRCDXYHTWTNR-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000011152 fibreglass Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000013517 stratification Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- IYQYZZHQSZMZIG-UHFFFAOYSA-N tricyclo[5.2.1.0(2.6)]deca-3,8-diene, 4.9-dimethyl Chemical compound C1C2C3C=C(C)CC3C1C=C2C IYQYZZHQSZMZIG-UHFFFAOYSA-N 0.000 description 1
- 238000011179 visual inspection Methods 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
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
- C08L71/12—Polyphenylene oxides
-
- 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
- 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
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- B32B2307/00—Properties of the layers or laminate
- B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
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- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/306—Resistant to heat
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- B32B2457/08—PCBs, i.e. printed circuit boards
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- C08J2371/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
- C08J2371/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C08J2371/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
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- C08J2425/02—Homopolymers or copolymers of hydrocarbons
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- C08J2435/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Derivatives of such polymers
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Abstract
The application provides a resin composition, a compound, a prepreg, an electric copper-clad plate, a preparation method and application thereof, and relates to the technical field of high polymer materials, wherein the resin composition comprises the following components in parts by mass: 10-30 parts of BVPE compound, 40-80 parts of polyphenyl ether resin and 0.01-3 parts of initiator, wherein the BVPE compound is selected from one or more of modified or unmodified BVPE polymers. The application also provides a preparation method of the resin composition, a BVPE compound, a preparation method of the BVPE compound, a prepreg based on the resin composition, an electric copper-clad plate and a preparation method of the electric copper-clad plate. The application provides a resin composition capable of improving dielectric property and heat resistance of products and application of the resin composition in circuit boards such as prepregs, electric copper-clad plates and the like, and has wide application prospect.
Description
Technical Field
The application relates to the technical field of high polymer materials, in particular to a resin composition, a compound, a prepreg, an electric copper-clad plate and a preparation method and application thereof.
Background
With the rapid development of electronic technology, high-capacity computer systems and electronic products such as communication base stations, servers, storage devices and the like have increasingly high requirements for high-frequency signal transmission. With the clear national proposals to accelerate 5G network deployment, the emphasis is on building 5G network systems, and the demands for this aspect will also be increasing in the future. 5G has higher requirements on the copper-clad plate due to high transmission rate and high reliability. However, the loss of the transmission of the electric signal increases with the increase of the transmission frequency of the signal, which further reduces the reliability of the signal transmission. Therefore, the dielectric loss factor of the substrate must be further reduced at high frequency and high transmission rate.
Currently, the printed circuit board uses polyphenylene oxide resin (PPO, or called polyphenylene oxide resin) to lower the dielectric constant D k and dielectric dissipation factor D f of the substrate, and is used in the middle-high end copper clad laminate and the printed circuit board due to its low dielectric dissipation and good heat resistance, environmental reliability, but the dielectric dissipation is insufficient at even higher frequencies. Therefore, further development of a resin composition having a lower dielectric dissipation factor D f is required as an active development target in the current industry.
In order to meet the requirement of high dielectric properties, hydrocarbon resin systems are generally adopted for resins in the existing printed circuit boards. The hydrocarbon resin mainly comprises polybutadiene, polystyrene, polypropylene, butadiene-styrene copolymer and other materials, has a self dielectric constant of 2.4-2.8 and a dielectric loss of 0.0002-0.0006, and has excellent electrical property; in consideration of factors such as impregnation property and heat resistance, hydrocarbon resin with low molecular weight is generally adopted, so that the copper-clad substrate with low dielectric property and excellent dimensional stability is prepared. However, the surface of the prepreg prepared from the hydrocarbon resin with low molecular weight is sticky, and defects are caused on the surface of the prepreg in the subsequent rolling, stacking and pressing processes, so that the processability of the copper-clad plate substrate is affected, and therefore, a new resin system with low dielectric property, which can be used in the field of printed circuit boards, needs to be provided.
Disclosure of Invention
The application aims to provide a resin composition which can be used in the field of printed circuit boards to improve dielectric properties of products.
It is still another object of the present application to provide a method for preparing a resin composition system.
It is a further object of the present application to provide a compound.
It is still another object of the present application to provide a process for the preparation of the compound.
It is still another object of the present application to provide a prepreg.
Still another object of the present application is to provide a method for preparing a prepreg.
Still another object of the present application is to provide an electrical copper clad laminate.
The application further aims at providing a preparation method of the electric copper-clad plate.
The application further aims to provide an application of the resin composition, the compound, the prepreg and the electric copper-clad plate in the field of circuit board preparation.
In order to achieve the above object, the present application provides the following technical solutions:
in a first aspect, the application provides a resin composition comprising the following components in parts by weight:
10 to 30 parts of BVPE compound
40-80 Parts of polyphenyl ether resin
Initiator 0.01-3 parts
Wherein the BVPE compound is selected from one or more of modified or unmodified BVPE polymers.
Further, in some embodiments of the application, the unmodified BVPE polymer is an oligomer of BVPE; the chemical structural formula of the oligomer of BVPE is shown as formula I:
Wherein n is selected from natural numbers of 1 to 10; and/or
The modified compound adopted by the modified BVPE polymer is selected from one or more of substituted or unsubstituted dicyclopentadiene, substituted or unsubstituted dicyclopentadiene oligomer, substituted or unsubstituted stilbene, substituted or unsubstituted styrene oligomer, substituted or unsubstituted vinyl-containing benzoxazine resin and substituted or unsubstituted maleimide compound.
Further, in some embodiments of the present application, the substituted dicyclopentadiene is selected from any one of methyl dicyclopentadiene dimer, diethyl dicyclopentadiene; and/or
The substituted stilbene is selected from any one of 2-methyl stilbene, 4-methyl stilbene, ethyl stilbene, propyl stilbene, isopropyl stilbene and hexyl stilbene; and/or
The substituted stilbene oligomer is selected from any one of 2-methyl stilbene oligomer, 4-methyl stilbene oligomer, ethyl stilbene oligomer, propyl stilbene oligomer, isopropyl stilbene oligomer and hexyl stilbene oligomer; and/or
The substituted styrene is selected from any one of methyl styrene, ethyl styrene, propyl styrene, isopropyl styrene, hexyl styrene and bis [ (4-vinyl phenyl) methoxy ] -tetramethyl biphenyl; and/or
The substituted styrene oligomer is selected from any one of methyl styrene oligomer, ethyl styrene oligomer, propyl styrene oligomer, isopropyl styrene oligomer and hexyl styrene oligomer; and/or
The benzoxazine in the substituted vinyl-containing benzoxazine resin is selected from any one of a mono-benzoxazine ring or a bis-benzoxazine ring; and/or
Maleimide compounds contain at least two imide ring groups or contain double bonds.
Further, in some embodiments of the present application, the benzoxazine is selected from one or more of bisphenol A type benzoxazine, bisphenol F type benzoxazine, phenolphthalein type benzoxazine, dicyclopentadiene type benzoxazine, phosphorous DOPO type benzoxazine.
Further, in some embodiments of the present application, the benzoxazine has a chemical formula selected from the group consisting of
Any one of them;
Wherein R 1、R3 is independently selected from (X=0 or 1), phenyl. R 2 is selected from any one of H, alkyl containing 1-6 carbon atoms, phenyl, epoxy, amino and nitro; r 4 is selected from any one of phenyl and nitrobenzene; r 5 is any one of methoxy; r 6 is selected from any one of methylene, isopropyl, oxygen atom and carbonyl; r 7 is selected from any one of hydrogen and allyl; r 8 is selected from any one of methylene, oxygen atom and the like; and/or
The chemical structural formula of the maleimide compound is selected from
Any one of them;
Wherein R 9 is selected from -CH2-、-C2H4-、C3H6-、-C4H8-、-C5H10-、
Any one of them;
R 10～R18 is each independently selected from the group consisting of-H, alkyl groups containing 1 to 15 carbon atoms, phenyl groups, and, Any one of them;
wherein i is a natural number of 1 to 10.
Further, in some embodiments of the application, the modified BVPE polymer is selected from one or more of the compounds having the chemical structural formulas shown in formulas II-IX; the chemical structural formula of the compound shown in the formulas II to IX is as follows:
Wherein a, b, c, d, e, f, g, i, j, k, p, q, r, s, t is independently selected from natural numbers of 1 to 10;
Wherein R 1、R3 is independently selected from (H=0 or 1), phenyl. R 2 is selected from any one of H, alkyl containing 1-6 carbon atoms, phenyl, epoxy, amino and nitro; r 5 is any one of methoxy; r 6 is selected from any one of methylene, isopropyl, oxygen atom and carbonyl; r 7 is selected from any one of hydrogen and allyl; r 8 is selected from any one of methylene, oxygen atom and the like; r 9 is selected from -CH2-、-C2H4-、C3H6-、-C4H8-、-C5H10-、 Any one of them;
The R 10 is selected from-H, alkyl group containing 1-15 carbon atoms, phenyl group, Any one of them.
Further, in some embodiments of the present application, the polyphenylene ether resin has a chemical formula as shown in formula X:
Wherein X is any one of methylene, oxygen atom, carbonyl and isopropyl;
u and v are independently selected from natural numbers of 1-10.
Further, in some embodiments of the application, the initiator is an initiator that promotes free radical polymerization of carbon-carbon unsaturation and double bonds at 130-180 ℃.
Further, in some embodiments of the application, the initiator is selected from one or more of peroxides.
Further, in some embodiments of the application, the peroxide is selected from any one of di-tert-butyl peroxide, tert-butyl hydroperoxide, cumene hydroperoxide; and/or
Further, in some embodiments of the present application, 10 to 50 parts by mass of a filler is further included in the resin composition; and/or;
the resin composition further comprises 30-200 parts by mass of a first solvent;
Further, in some embodiments of the application, the filler is an organic filler and/or an inorganic filler.
Further, in some embodiments of the present application, the organic filler is selected from one or more of polytetrafluoroethylene powder, polyphenylene sulfide; and/or
The inorganic filler is selected from one or more of silicon dioxide, synthetic silicon dioxide, spherical silicon dioxide, fused silicon dioxide, aluminum hydroxide, aluminum oxide and boron nitride.
Further, in some embodiments of the application, the first solvent is selected from one or more of methanol, ethanol, ethylene glycol monomethyl ether, acetone, butanone, dimethylformamide, dimethylacetamide, methyl isobutyl ketone, methoxy acetone, toluene, cyclohexanone, methyl cellosolve, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, xylene.
In a second aspect, the present application also discloses a method for preparing a resin composition system, comprising:
providing the components of the resin composition according to the first aspect;
Mixing BVPE compound, polyphenyl ether resin, solvent and/or filler;
and adding an initiator, and dispersing to obtain a resin composition system.
In a third aspect, the present application also provides a compound having a chemical structural formula as shown in any one of formulas I to IX:
Wherein a, b, c, d, e, f, g, i, j, k, n, p, q, r, s, t is independently selected from natural numbers of 1 to 10;
Wherein R 1、R3 is independently selected from (X=0 or 1), phenyl. R 2 is selected from any one of H, alkyl containing 1-6 carbon atoms, phenyl, epoxy, amino and nitro; r 5 is any one of methoxy; r 6 is selected from any one of methylene, isopropyl, oxygen atom and carbonyl; r 7 is selected from any one of hydrogen and allyl; r 8 is selected from any one of methylene, oxygen atom and the like; r 9 is selected from -CH2-、-C2H4-、C3H6-、-C4H8-、-C5H10-、 Any one of them;
The R 10 is selected from-H, alkyl group containing 1-15 carbon atoms, phenyl group, Any one of them.
In a fourth aspect, the present application also provides a method for preparing a compound comprising:
providing compound 1, compound 2, a second solvent, and a second initiator;
Mixing a compound, a compound 2, a second solvent and a second initiator, reacting for 20-300 min at 60-120 ℃, and cooling to obtain the compound;
wherein, the compound 1 is BVPE;
The compound 2 is selected from BVPE, stilbene, styrene,
One or more of the following;
Wherein R 1、R3 is independently selected from (X=0 or 1), phenyl. R 2 is selected from any one of H, alkyl containing 1-6 carbon atoms, phenyl, epoxy, amino and nitro; r 5 is any one of methoxy; r 6 is selected from any one of methylene, isopropyl, oxygen atom and carbonyl; r 7 is selected from any one of hydrogen and allyl; r 8 is selected from any one of methylene, oxygen atom and the like; r 9 is selected from -CH2-、-C2H4-、C3H6-、-C4H8-、-C5H10-、 Any one of them;
The R 10 is selected from-H, alkyl group containing 1-15 carbon atoms, phenyl group, Any one of them;
i is selected from natural numbers of 1 to 10.
Further, in some embodiments of the application, the mass ratio of compound 1 to compound 2 is 0.9:1 to 1.2:1, a step of; and/or
The mass ratio of the second solvent to the compound 1 is 1:1 to 1:4, a step of; and/or
The mass ratio of the second initiator to the compound 1 is 0.001:100 to 0.2:100.
Further, in some embodiments of the application, the second solvent is selected from one or more of toluene, butanone, cyclohexanone, xylene, N-dimethylformamide; and/or
The second initiator is selected from any one of dimethylbenzoyl peroxide or 1, 1-bis (tertiary butyl peroxy) -3, 5-trimethylcyclohexane.
In a fifth aspect, the present application also provides a prepreg comprising an attachment,
The attachments are obtained by solidifying a resin composition system prepared by the resin composition according to the first aspect or the resin composition system preparation method according to the second aspect.
Further, in some embodiments of the application, the prepreg further comprises a reinforcing material;
the attachment adheres to the reinforcing material.
Further, in some embodiments of the present application, the reinforcing material is selected from at least one of natural fibers, organic synthetic fibers, organic fabrics, and inorganic fabrics.
In a sixth aspect, the present application also provides a method for preparing a prepreg, including:
providing a reinforcing material and a resin composition according to the first aspect or a resin composition system prepared by a method for preparing a resin composition system according to the second aspect;
And (3) adhering components in the resin composition or the resin composition system to the surface of the reinforcing material, and semi-curing to obtain the prepreg.
Further, in some embodiments of the present application, adhering the components of the resin composition or the resin composition system to the surface of the reinforcing material comprises:
Impregnating the reinforcing material with the resin composition or the resin composition system for 0.5-1min.
Further, in some embodiments of the application, the semi-curing comprises:
Heat treating the reinforcing material with the components of the resin composition or the resin composition system attached thereto at 100-200 ℃ for 1-10min.
In a seventh aspect, the application further provides an electric copper-clad plate, which comprises the prepreg according to the fifth aspect or the prepreg obtained by the preparation method of the prepreg according to the sixth aspect.
Further, in some embodiments of the present application, the electrical copper-clad plate further comprises a copper foil;
the copper foil is coated on one side or both sides of the prepreg.
In an eighth aspect, the present application further provides a method for preparing an electrical copper-clad plate, including:
providing a copper foil and the prepreg according to the fifth aspect or the prepreg obtained by the preparation method of the prepreg according to the sixth aspect;
the copper foil is repeated on one side or two sides of the prepreg to obtain a semi-finished device;
pressing the semi-finished product device for 5-10 hours by using a pressing process to obtain the electric copper-clad plate;
the lamination process comprises a first lamination section and a second lamination section; the first pressing section comprises the steps of heating to 170-190 ℃ at a heating rate of 4-6 ℃/min, heating to 5MPa at a heating rate of 0.05-0.2MPa/min, and pressing the semi-finished device for 2-4 h;
the second lamination section includes: and pressing the semi-finished device passing through the first pressing section at 200-240 ℃ and 5MPa for 3-6 h.
The ninth aspect of the present application further provides a resin composition system prepared by the resin composition according to the first aspect or the resin composition system preparation method according to the second aspect, a compound prepared by the compound according to the third aspect, the compound prepared by the compound preparation method according to the fourth aspect, a prepreg according to the fifth aspect or a prepreg obtained by the prepreg preparation method according to the sixth aspect, and an application of the electric copper-clad plate obtained by the electric copper-clad plate preparation method according to the seventh aspect or the electric copper-clad plate obtained by the electric copper-clad plate preparation method according to the eighth aspect in the circuit board preparation field.
The application provides a resin composition, which is prepared by adding BVPE or BVPE compounds into polyphenyl ether resin, so that the prepared resin has excellent dielectric property, the solubility of BVPE monomers is improved to limit the application of the BVPE monomers, the amount of BVPE which can be added into the resin composition is increased, the application of BVPE in prepregs, electric copper-clad plates, circuit boards and the like is further increased, and the improvement and optimization of the dielectric property of the BVPE in prepregs, electric copper-clad plates, circuit boards and the like are fully utilized. In addition, the polyphenylene ether resin and the BVPE or BVPE compound are adopted in the resin composition provided by the application for copolymerization, and the double bond structure contained in the molecular structure of the resin composition not only can be used as a reactive point, but also can increase the crosslinking point in the curing process of the resin, so that the crosslinking density of the resin is improved, and the heat resistance of a product is improved; meanwhile, after BVPE containing hydrocarbon chain segments is introduced into the polyphenyl ether resin, the content of the hydrocarbon chain segments in the resin composition can be increased, and the dielectric constant of a product formed by the resin composition is reduced, so that the dielectric loss of the obtained prepreg, the electric copper-clad plate and the circuit board is lower, and the prepreg, the electric copper-clad plate and the circuit board have better dielectric properties.
The application provides a preparation method of a resin composition system, which is simple and easy to industrialize.
The application provides a compound, which is a polymer obtained by modifying BVPE with a compound containing hydrocarbon chain segments, improves the molecular weight of BVPE, improves the solubility of BVPE in a resin composition and the content of the hydrocarbon chain segments in single molecules, and improves the addition amount of the compound in the resin composition, thereby reducing the dielectric constant and dielectric loss of the resin based on the compound and ensuring that prepregs, electric copper-clad plates and circuit boards based on the compound have good dielectric properties. In addition, the benzoxazine or maleimide modified BVPE can also be introduced into the compound to improve the dimensional stability, heat resistance and glass transition temperature of the resin composition, so that the obtained prepreg, electric copper-clad plate and circuit board have good dimensional stability, heat resistance and glass transition temperature.
The application also provides a preparation method of the compound, which is simple and easy to industrialize.
The application provides a prepreg, which takes a resin compound or a resin compound system with BVPE or BVPE compounds added into polyphenyl ether resin as a raw material attached to a base material, improves the heat resistance of the prepreg, has excellent dielectric properties, can be applied to high-speed high-frequency fields such as 5G networks and the like, and has wide application prospect.
The application provides a preparation method of a prepreg, which is simple and easy to industrialize.
The application provides an electric copper-clad plate which takes a prepreg which has excellent heat resistance and excellent dielectric property as a raw material, so that the electric copper-clad plate has excellent dielectric property and excellent heat resistance.
The application provides a preparation method of an electric copper-clad plate, which is simple and easy to industrialize.
Detailed Description
The aspects of the present application will be described more fully hereinafter with reference to the accompanying drawings, in which some, but not all embodiments of the application are shown. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to be within the scope of the application.
In a first aspect, embodiments of the present application provide a first aspect, and the present application provides a resin composition, including the following components in parts by weight:
10 to 30 parts of BVPE compound
40-80 Parts of polyphenyl ether resin
Initiator 0.01-3 parts
Wherein the BVPE compound is selected from one or more of modified or unmodified BVPE polymers.
BVPE (P, P' -divinyl-1, 2-diphenylethane) is an olefin monomer with hydrocarbon chain segments, has good optimization effect on dielectric properties and heat resistance of circuit board devices such as prepregs, electric copper-clad plates and the like, and is particularly an oligomer of BVPE. However, the solubility of the BVPE monomer is poor, and it is difficult to increase the addition amount of the BVPE monomer in circuit board devices such as prepregs and electric copper-clad plates, so that the improvement effect of the BVPE monomer on the dielectric properties and heat resistance of the circuit board devices such as prepregs and electric copper-clad plates is limited, and therefore, little research progress is made in applying the BVPE to the circuit board devices such as prepregs and electric copper-clad plates. In order to solve the technical problem, the application provides a resin composition, which is prepared by adding BVPE or BVPE compounds into polyphenyl ether resin, and using BVPE or BVPE compounds and double bond structures contained in the polyphenyl ether resin as reactive points and crosslinking points, so as to improve the crosslinking density of the resin obtained by curing the resin composition and improve the heat resistance of the resin obtained by curing the resin composition; meanwhile, the addition amount of BVPE or BVPE compounds which can be added into the resin composition is increased, the effect of reducing the dielectric constant and dielectric loss of circuit board devices such as prepregs, electric copper-clad plates and the like is improved, the dielectric performance of the obtained circuit board devices such as prepregs, electric copper-clad plates and the like is improved, and the obtained circuit board devices such as prepregs, electric copper-clad plates and the like can be better applied to the high-frequency and high-speed field.
In some embodiments, the unmodified BVPE polymer is an oligomer of BVPE; the chemical structural formula of the oligomer of BVPE is shown as formula I:
Wherein n is selected from natural numbers of 1 to 10; and/or
The modified compound adopted by the modified BVPE polymer is selected from one or more of substituted or unsubstituted dicyclopentadiene, substituted or unsubstituted dicyclopentadiene oligomer, substituted or unsubstituted stilbene, substituted or unsubstituted styrene oligomer, substituted or unsubstituted vinyl-containing benzoxazine resin and substituted or unsubstituted maleimide compound.
The modified or unmodified BVPE polymer is an oligomer containing BVPE, because the modified compound is introduced by double bond initiation during the modification process, and the BVPE oligomer is obtained. In the initiation process, the dosage of the initiator is controlled at the same time, so that the poor processability caused by the excessively high polymerization degree is avoided.
In some embodiments, the substituted dicyclopentadiene is selected from any of methylcyclopentadiene dimer, diethyldicyclopentadiene; and/or
The substituted stilbene is selected from any one of 2-methyl stilbene, 4-methyl stilbene, ethyl stilbene, propyl stilbene, isopropyl stilbene and hexyl stilbene; and/or
The substituted stilbene oligomer is selected from any one of 2-methyl stilbene oligomer, 4-methyl stilbene oligomer, ethyl stilbene oligomer, propyl stilbene oligomer, isopropyl stilbene oligomer and hexyl stilbene oligomer; and/or
The substituted styrene is selected from any one of methyl styrene, ethyl styrene, propyl styrene, isopropyl styrene, hexyl styrene and bis [ (4-vinyl phenyl) methoxy ] -tetramethyl biphenyl; and/or
The substituted styrene oligomer is selected from any one of methyl styrene oligomer, ethyl styrene oligomer, propyl styrene oligomer, isopropyl styrene oligomer and hexyl styrene oligomer; and/or
The benzoxazine in the substituted vinyl-containing benzoxazine resin is selected from any one of a mono-benzoxazine ring or a bis-benzoxazine ring; and/or
Maleimide compounds contain at least two imide ring groups or contain double bonds.
In some embodiments, the benzoxazine is selected from one or more of bisphenol A type benzoxazine, bisphenol F type benzoxazine, phenolphthalein type benzoxazine, dicyclopentadiene type benzoxazine, phosphorous DOPO type benzoxazine.
In some embodiments, the benzoxazine has a chemical formula selected from the group consisting of:
Any one of them;
Wherein R 1、R3 is independently selected from (X=0 or 1), phenyl. R 2 is selected from any one of H, alkyl containing 1-6 carbon atoms, phenyl, epoxy, amino and nitro; r 4 is selected from any one of phenyl and nitrobenzene; r 5 is any one of methoxy; r 6 is selected from any one of methylene, isopropyl, oxygen atom and carbonyl; r 7 is selected from any one of hydrogen and allyl; r 8 is selected from any one of methylene, oxygen atom and the like; and/or
The chemical structural formula of the maleimide compound is selected from
Any one of them;
Wherein R 9 is selected from -CH2-、-C2H4-、C3H6-、-C4H8-、-C5H10-、
Any one of them;
R 10～R18 is each independently selected from the group consisting of-H, alkyl groups containing 1 to 15 carbon atoms, phenyl groups, and, Any one of them;
wherein i is a natural number of 1 to 10.
In some embodiments, BVPE-based compounds may be classified in the present application as (1) BVPE oligomers, modified BVPEs substituted or being unsubstituted dicyclopentadiene modified BVPEs, oligomers substituted or being modified BVPEs formed from unsubstituted dicyclopentadiene and BVPEs, modified BVPEs substituted or being unsubstituted stilbene modified BVPEs, oligomers substituted or being modified BVPEs formed from unsubstituted stilbene and BVPEs; BVPE and diphenylmethane (BVPM), BVPE and cyclohexane stilbene (BVPH), an oligomer of modified BVPE formed from substituted or unsubstituted styrene and BVPE, an oligomer of modified BVPE substituted or unsubstituted styrene modified BVPE, (2) a modified BVPE oligomer of modified BVPE of substituted or unsubstituted vinyl containing benzoxazine resin, and (3) a modified BVPE oligomer of modified BVPE of substituted or unsubstituted maleimide compound. In the present application, the BVPE compound in the resin composition is selected from any one or more of the compounds (1), (2) and (3), and when the BVPE compound in the resin composition is selected from any one or more of the compounds (1), (2) and (3), the ratio of the various BVPE compounds can be adjusted as required.
In some embodiments, when the BVPE-based compound in the resin composition is selected from a plurality of the (1), (2), and (3), the (1) th compound is present in the resin composition at a ratio greater than the (2) th compound or the (3) th compound. This is because the compound (1) is mainly hydrocarbon resin, the resin has a low dielectric constant, and other elements are introduced into the compound (2) and the compound (3), which have an adverse effect on the dielectric constant, so that the compound (1) is preferably added in a larger proportion, and the effect of the compound (2) and/or the compound (3) on the dielectric constant is reduced.
In some embodiments, when the BVPE compound in the resin composition is selected from a plurality of BVPE compounds in (1), (2) and (3), the mass ratio of the (1) th compound to the (2) th compound is 2:1-10:1; or (b)
The mass ratio of the (1) compound to the (3) compound is 2:1-10:1;
The mass ratio of the (1) compound to the (2) compound to the (3) compound is 4:1:1-20:1:1.
In some embodiments, the modified BVPE polymer is selected from one or more of the compounds having the chemical structural formulas shown in formulas II-IX; the chemical structural formula of the compound shown in the formulas II to IX is as follows:
Wherein a, b, c, d, e, f, g, i, j, k, p, q, r, s, t is independently selected from natural numbers of 1 to 10;
Wherein R 1、R3 is independently selected from (H=0 or 1), phenyl. R 2 is selected from any one of H, alkyl containing 1-6 carbon atoms, phenyl, epoxy, amino and nitro; r 5 is any one of methoxy; r 6 is selected from any one of methylene, isopropyl, oxygen atom and carbonyl; r 7 is selected from any one of hydrogen and allyl; r 8 is selected from any one of methylene, oxygen atom and the like; r 9 is selected from -CH2-、-C2H4-、C3H6-、-C4H8-、-C5H10-、 Any one of them;
The R 10 is selected from-H, alkyl group containing 1-15 carbon atoms, phenyl group, Any one of them.
In some embodiments, when the BVPE-based compound comprises a modified BVPE oligomer modified with a vinyl-containing benzoxazine resin, the modified BVPE oligomer modified with a vinyl-containing benzoxazine resin is preferably a compound of formula VI because of the lower dielectric constant of the benzoxazine of this type of structure.
In some embodiments, when the BVPE-based compound comprises a modified BVPE oligomer modified with a substituted or unsubstituted maleimide-based compound, the modified BVPE oligomer modified with a substituted or unsubstituted maleimide-based compound is preferably a compound of formula VIII because of the lower dielectric constant of such bismaleimides.
In some embodiments, the polyphenylene ether resin has a chemical formula as shown in formula X:
Wherein X is any one of methylene, oxygen atom, carbonyl and isopropyl;
u and v are independently selected from natural numbers of 1-10.
In some embodiments, the polyphenylene ether resin is selected from the polyphenylene ether resins having a model number SA 9000.
In some embodiments, the initiator is an initiator that promotes free radical polymerization of carbon-carbon unsaturation and double bonds at 130-180 ℃.
The initiator is selected from free radical high temperature polymerization initiator, and can promote the free radical polymerization reaction of carbon-carbon unsaturated bond and double bond at relatively high temperature to realize crosslinking, so that the obtained resin has high crosslinking density and good mechanical property.
In some embodiments, the initiator is selected from one or more of peroxide-based initiators.
In some embodiments, the peroxide is selected from any one of di-tert-butyl peroxide, tert-butyl hydroperoxide, cumene hydroperoxide;
in some embodiments, the initiator is di-t-butyl peroxide.
In some embodiments, the resin composition further comprises 10 to 50 parts by mass of a filler, preferably 20 to 40 parts by mass; and/or;
The resin composition further comprises 30 to 200 parts by mass of a first solvent, preferably 40 to 100 parts by mass.
In some embodiments, the filler is an organic filler and/or an inorganic filler.
In some embodiments, the inorganic filler is selected from one or more of a non-metal oxide, an inorganic salt.
In some embodiments, the organic filler is selected from one or more of polytetrafluoroethylene powder, polyphenylene sulfide; and/or
The inorganic filler is selected from one or more of silicon dioxide, synthetic silicon dioxide, spherical silicon dioxide, fused silicon dioxide, aluminum hydroxide, aluminum oxide and boron nitride.
Preferably, the filler is selected from silica, more preferably surface treated spherical silica. This is because the surface-treated spherical silica has better compatibility with the resin material.
In some embodiments, the first solvent is selected from one or more of methanol, ethanol, ethylene glycol monomethyl ether, acetone, butanone, dimethylformamide, dimethylacetamide, methyl isobutyl ketone, methoxyacetone, toluene, cyclohexanone, methyl cellosolve, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, xylene.
In a second aspect, the present application also discloses a method for preparing a resin composition system, comprising:
providing the components of the resin composition according to the first aspect;
Mixing BVPE compound, polyphenyl ether resin, a first solvent and/or filler;
and adding an initiator, and dispersing to obtain a resin composition system.
In some embodiments, mixing the BVPE-based compound, the polyphenylene ether resin, the first solvent, and/or the filler comprises:
Stirring for 10-60 min at 1000-2000 rpm to mix BVPE compound, polyphenyl ether resin, solvent and/or filler uniformly.
In some embodiments, dispersing comprises:
and dispersing and treating a system consisting of the BVPE compound, the polyphenyl ether resin, the solvent and/or the filler and the initiator for 10-60 min by using a mechanical stirring method.
In a third aspect, the present application also provides a compound having a chemical structural formula as shown in any one of formulas I to IX:
Wherein a, b, c, d, e, f, g, i, j, k, n, p, q, r, s, t is independently selected from natural numbers of 1 to 10;
Wherein R 1、R3 is independently selected from (X=0 or 1), phenyl. R 2 is selected from any one of H, alkyl containing 1-6 carbon atoms, phenyl, epoxy, amino and nitro; r 5 is any one of methoxy; r 6 is selected from any one of methylene, isopropyl, oxygen atom and carbonyl; r 7 is selected from any one of hydrogen and allyl; r 8 is selected from any one of methylene, oxygen atom and the like; r 9 is selected from -CH2-、-C2H4-、C3H6-、-C4H8-、-C5H10-、 Any one of them;
The R 10 is selected from-H, alkyl group containing 1-15 carbon atoms, phenyl group, Any one of them.
In a fourth aspect, the present application also provides a method for preparing a compound comprising:
providing compound 1, compound 2, a second solvent, and a second initiator;
Mixing a compound, a compound 2, a second solvent and a second initiator, reacting for 20-300 min at 60-120 ℃, and cooling to obtain the compound;
wherein, the compound 1 is BVPE;
The compound 2 is selected from BVPE, stilbene, styrene,
One or more of the following;
Wherein R 1、R3 is independently selected from (X=0 or 1), phenyl. R 2 is selected from any one of H, alkyl containing 1-6 carbon atoms, phenyl, epoxy, amino and nitro; r 5 is any one of methoxy; r 6 is selected from any one of methylene, isopropyl, oxygen atom and carbonyl; r 7 is selected from any one of hydrogen and allyl; r 8 is selected from any one of methylene, oxygen atom and the like; r 9 is selected from -CH2-、-C2H4-、C3H6-、-C4H8-、-C5H10-、 Any one of them;
The R 10 is selected from-H, alkyl group containing 1-15 carbon atoms, phenyl group, Any one of them;
i is selected from natural numbers of 1 to 10.
In some embodiments, the mass ratio of compound 1 to compound 2 is 0.9:1 to 1.2:1, a step of; and/or
The mass ratio of the second solvent to the compound 1 is 1:1 to 1:4, a step of; and/or
The mass ratio of the second initiator to the compound 1 is 0.001:100 to 0.2:100.
In some embodiments, the second solvent is selected from one or more of toluene, butanone, cyclohexanone, xylene, N-dimethylformamide; toluene is preferred; and/or
The second initiator is selected from any one of dimethylbenzoyl peroxide or 1, 1-bis (tertiary butyl peroxy) -3, 5-trimethylcyclohexane.
The second initiator is a low-temperature free radical initiator which can promote the crosslinking reaction of BVPE monomer and/or modified substance at 80-120 ℃, so that the BVPE compound obtained by crosslinking still has good reactivity and fluidity, and unreacted unsaturated double bonds exist, and when the polyphenylene ether resin is crosslinked and cured at high temperature, the polyphenylene ether resin can be further cured and crosslinked under the action of the high-temperature initiator, and the heat resistance of the resin is improved.
In a fifth aspect, the present application also provides a prepreg comprising an attachment,
The attachments are obtained by solidifying a resin composition system prepared by the resin composition according to the first aspect or the resin composition system preparation method according to the second aspect.
In some embodiments, the prepreg further comprises a reinforcing material;
the attachment adheres to the reinforcing material.
In some embodiments, the reinforcing material is selected from at least one of natural fibers, organic synthetic fibers, organic fabrics, and inorganic fabrics.
In some embodiments, the reinforcing material is preferably fiberglass cloth, and still more preferably open or flat cloth.
In a sixth aspect, the present application also provides a method for preparing a prepreg, including:
providing a reinforcing material and a resin composition according to the first aspect or a resin composition system prepared by a method for preparing a resin composition system according to the second aspect;
And (3) adhering components in the resin composition or the resin composition system to the surface of the reinforcing material, and semi-curing to obtain the prepreg.
In some embodiments, attaching the components of the resin composition or the resin composition system to the surface of the reinforcement material comprises:
Impregnating the reinforcing material with the resin composition or the resin composition system for 0.5-1min.
In some embodiments, the semi-curing comprises:
Heat treating the reinforcing material with the components of the resin composition or the resin composition system attached thereto at 100-200 ℃ for 1-10min.
In a seventh aspect, the application further provides an electric copper-clad plate, which comprises the prepreg according to the fifth aspect or the prepreg obtained by the preparation method of the prepreg according to the sixth aspect.
In some embodiments, the electrical copper-clad plate further comprises a copper foil;
the copper foil is coated on one side or both sides of the prepreg.
In an eighth aspect, the present application further provides a method for preparing an electrical copper-clad plate, including:
providing a copper foil and the prepreg according to the fifth aspect or the prepreg obtained by the preparation method of the prepreg according to the sixth aspect;
the copper foil is repeated on one side or two sides of the prepreg to obtain a semi-finished device;
pressing the semi-finished product device for 5-10 hours by using a pressing process to obtain the electric copper-clad plate;
the lamination process comprises a first lamination section and a second lamination section; the first pressing section comprises the steps of heating to 170-190 ℃ at a heating rate of 4-6 ℃/min, heating to about 5MPa at a heating rate of 0.05-0.2MPa/min, and pressing the semi-finished device for 2-4 hours;
the second lamination section includes: and pressing the semi-finished device passing through the first pressing section at 200-240 ℃ and 5MPa for 3-6 h.
The ninth aspect of the present application further provides a resin composition system prepared by the resin composition according to the first aspect or the resin composition system preparation method according to the second aspect, a compound prepared by the compound according to the third aspect, the compound prepared by the compound preparation method according to the fourth aspect, a prepreg according to the fifth aspect or a prepreg obtained by the prepreg preparation method according to the sixth aspect, and an application of the electric copper-clad plate obtained by the electric copper-clad plate preparation method according to the seventh aspect or the electric copper-clad plate obtained by the electric copper-clad plate preparation method according to the eighth aspect in the circuit board preparation field. In some embodiments, the divalent hydrocarbon group may be selected from any one of a substituted or unsubstituted divalent alkyl group, a divalent alkylene group, a divalent alkyne group, a divalent aromatic hydrocarbon group, a divalent cycloalkyl group.
The technical solutions of the present invention will be clearly and completely described in connection with the embodiments, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
BVPE used in the following specific examples was purchased from shandongxing cis new materials limited;
toluene used in the following specific examples was purchased from Colon Chemicals Co., ltd;
The xylenyl peroxide used in the following specific examples was purchased from Colon Chemicals Co., ltd;
the polyphenylene ether resin used in the following specific examples was from SABIC company, and its model was SA9000;
The silica used in the following specific examples was purchased from Colon Chemicals, inc. of Chemicals, inc.;
The di-t-butyl peroxide used in the following specific examples was purchased from Colon Chemicals, inc., nano-scale;
the diaminodiphenylmethane maleimide resin used in the following specific examples was obtained from Chengdu Corp. High molecular technology Co., ltd, and was designated as CM5000;
styrene used in the following specific examples was purchased from Colon Chemicals Co., ltd;
Bisphenol A-allylamine type benzoxazine compound used in the following specific examples was purchased from Chengdu Corp. High molecular technology Co., ltd, model CB2100;
The glass fiber cloth used in the following specific examples was purchased from Langfang An Lang sealing materials, inc. under the model number 7628.
Example 1
The embodiment provides a preparation method of BVPE compounds, wherein the chemical structural formula of the BVPE compounds is shown as follows:
the preparation method comprises the following steps:
in a reactor equipped with a stirrer, a condenser and a thermometer, 100g of BVPE,100g of toluene and 0.01g of dibenzoyl peroxide were charged. Heating to 90 ℃, prepolymerizing for 100min, and cooling to obtain a product (hereinafter referred to as a compound A) with a chemical structural formula shown in the formula, wherein n=10-20;
The compound A is prepared into a resin composition system according to the following formula, wherein the formula of the resin composition in the resin composition system is as follows:
30 parts of compound A, 80 parts of polyphenyl ether resin, 30 parts of silicon dioxide, 0.01 part of di-tert-butyl peroxide and 66 parts of toluene.
According to the above formulation, the compound A, the polyphenylene ether resin, the silica, the di-t-butyl peroxide and the toluene are uniformly dispersed in the butanone by stirring at a high speed of 1000 to 2000rpm, thereby obtaining a resin composition system A.
Taking a plurality of parts of glass fiber cloth as a reinforcing material, immersing the glass fiber cloth in the resin composition system A to enable the glass fiber cloth to be immersed, carrying out heat treatment on the reinforcing material after the immersion is completed at 140 ℃ for 5min, removing toluene solvent, and drying to obtain a plurality of parts of prepregs A.
And 2 copper foils are taken, the obtained 5 prepregs A are laminated to form a prepreg layer A, then copper foils are respectively arranged on two sides of the prepreg layer A, the prepreg layer A is placed at a temperature rising rate of 4 ℃/min from room temperature to 180 ℃, the pressure is increased from 0.5MPa to 5MPa at a rate of 0.1MPa/min, and the lamination is kept for 3 hours. And heating to 220 ℃, keeping pressing for 3 hours, releasing pressure and naturally cooling to obtain the electric copper-clad plate A.
Example 2
The embodiment provides a preparation method of BVPE compounds, wherein the chemical structural formula of the BVPE compounds is shown as follows:
the preparation method comprises the following steps:
In a reactor equipped with stirrer, condenser, thermometer, 50g BVPE,50g bisphenol A-allylamine type benzoxazine, 100g toluene and 0.01g xylene formyl peroxide. Heating to 90 ℃, prepolymerizing for 100min, and cooling to obtain a product (hereinafter referred to as a compound B) with a chemical structural formula shown in the specification, wherein n=1-10 and r=1-10;
The compound B is used for replacing the compound A, a resin composition system B is obtained according to the formula and the steps shown in the embodiment 1, a prepreg is prepared by using the resin composition system B and adopting the same steps as the embodiment 1, the prepreg B is obtained, and the electric copper-clad plate B is obtained by using the prepreg B and adopting the same steps as the embodiment 1.
The other components of the resin composition system B except for the compound B were the same as those of example 1.
Example 3
The embodiment provides a preparation method of BVPE compounds, wherein the chemical structural formula of the BVPE compounds is shown as follows:
the preparation method comprises the following steps:
In a reactor equipped with stirrer, condenser, thermometer, 50g BVPE,50g diaminodiphenylmethane bismaleimide, 100g toluene and 0.01g xylene-carbonyl peroxide. Heating to 90 ℃, prepolymerizing for 100min, and cooling to obtain a product (hereinafter referred to as a compound C) with a chemical structural formula shown in the specification, wherein n=1-10 and p=1-10;
The compound C is used for replacing the compound A, a resin composition system C is obtained according to the formula and the steps shown in the embodiment 1, a prepreg is prepared by using the resin composition system C and adopting the same steps as the embodiment 1, the prepreg C is obtained, and the electric copper-clad plate C is obtained by using the prepreg C and adopting the same steps as the embodiment 1.
The other components of the resin composition system C except for the compound B were the same as those of example 1.
Example 4
The embodiment provides a preparation method of BVPE compounds, wherein the chemical structural formula of the BVPE compounds is shown as follows:
the preparation method comprises the following steps:
In a reactor equipped with stirrer, condenser, thermometer, 50g BVPE,50g styrene, 100g toluene and 0.01g xylene formyl peroxide. Heating to 90 ℃, prepolymerizing for 100min, and cooling to obtain a product with a chemical structural formula shown as the above formula (hereinafter referred to as a compound D), wherein n=1-10, and I=1-10;
The compound D is used for replacing the compound A, a resin composition system D is obtained according to the formula and the steps shown in the embodiment 1, a prepreg is prepared by using the resin composition system D and adopting the same steps as the embodiment 1, the prepreg D is obtained, and the electric copper-clad plate D is obtained by using the prepreg D and adopting the same steps as the embodiment 1.
The other components of the resin composition system D except for the compound B were the same as those of example 1.
Example 5
In comparison with example 1, in this example, BVPE was used instead of compound a, and a resin composition system E was obtained according to the formulation and procedure as shown in example 1, and a prepreg was prepared by using the resin composition system E and the same procedure as in example 1, to obtain a prepreg E, and then an electric copper-clad plate E was obtained by using the prepreg E and the same procedure as in example 1.
The other components of the resin composition system E except for the compound B were the same as those of example 1.
Example 6
The compound a obtained in example 1 was used to prepare a resin composition system in which the resin composition had the following formula:
50 parts of compound A, 80 parts of polyphenyl ether resin, 30 parts of silicon dioxide, 0.01 part of di-tert-butyl peroxide and 75 parts of toluene.
According to the above formulation, the compound A, the polyphenylene ether resin, the silica, the di-t-butyl peroxide and the toluene are uniformly dispersed in the butanone by stirring at a high speed of 1000 to 2000rpm, to obtain a resin composition system F.
And preparing a prepreg by using the resin composition system F according to the same steps as in the embodiment 1 to obtain the prepreg F, and preparing an electric copper-clad plate by using the prepreg F according to the same steps as in the embodiment 1 to obtain the electric copper-clad plate F.
Comparative example 1
In comparison with example 3, this comparative example uses bisphenol A-allylamine type benzoxazine instead of compound C, and a comparative system A was prepared in accordance with the formulation of the resin composition system in example 4;
using the comparative system A, comparative prepreg A and comparative copper-clad laminate A were prepared by the same preparation method as in example 1.
Comparative example 2:
In comparison with example 4, this comparative example uses diaminodiphenylmethane-type bismaleimide instead of compound D, and comparative system B was prepared in accordance with the formulation of the resin composition system in example 4;
Using comparative System B, comparative prepreg B and comparative copper-clad laminate B were prepared by the same preparation method as in example 1.
Comparative example 3:
In comparison with example 4, the styrene of this comparative example replaces compound D, and comparative system C was prepared in accordance with the formulation of the resin composition system in example 1;
using comparative System C, comparative prepreg C and comparative copper-clad laminate C were prepared by the same preparation method as in example 1.
The resin composition systems A to F and the comparative systems A to C obtained in examples 1 to 6 and comparative examples 1 to 3 were respectively tested for compatibility of components; the test results of the glass transition temperatures, copper foil peel strength, heat resistance, thermal decomposition temperature, thermal delamination time (T-288), dielectric constants, dielectric loss factors and resin system compatibility of the electric copper-clad plate A to the electric copper-clad plate F and the comparative electric copper-clad plate A to the comparative electric copper-clad plate C are shown in Table 1.
TABLE 1
The relevant standard base method adopted by the technical indexes in table 1 is as follows:
(1) Compatibility of each component of the glue solution: visual inspection
(2) Glass transition temperature (T g): according to differential scanning calorimetry, the measurement was carried out according to DSC method defined in IPC-TM-650.2.4.25
(3) Copper foil Peel Strength (PS): the peel strength of the metal cap layer was recorded as determined by the test method specified in IPC-TM-6502.4.8.
(4) Tin immersion heat resistance: the time for delamination of the bubbles of the sample was recorded using a 50X 50mm double sided copper sample immersed in a 288℃solder.
(5) Thermal decomposition temperature: determination according to the method specified in IPC-TM-6502.4.26
(6) Dielectric constant (D k): the measurement was performed according to the test method prescribed in IPC-TM-6502.5.5.9.
(7) Dielectric loss factor (D f): the measurement was performed according to the test method prescribed in IPC-TM-6502.5.5.9.
(8) Thermal stratification time T-288: the measurement was performed according to the method prescribed by IPC-TM-6502.4.24.
(9) Resin system compatibility: taking the cross section of the base material, observing microscopic uniformity of the cured resin under SEM, and if the resin agglomeration phenomenon occurs, obtaining incompatibility.
As can be seen from Table 1, compared with comparative examples 1 to 3, the electric copper-clad plates provided by examples 1 to 6 of the present application all have higher copper foil peel strength, lower dielectric constant, lower dielectric loss factor and higher thermal delamination time, and therefore, the resin composition provided by the present application is beneficial to improving the peel strength of the electric copper-clad plate, improving the heat resistance thereof, and reducing the dielectric constant and dielectric loss thereof, so that the obtained electric copper-clad plate has better dielectric property and heat resistance. Meanwhile, as can be seen from examples 1 and 6, the increase of the BVPE compound can further improve the copper foil peeling strength of the electric copper clad laminate and further reduce the dielectric constant and dielectric loss factor of the electric copper clad laminate, so that the addition of the BVPE compound has a positive effect on improving the dielectric property of the electric copper clad laminate, and the dielectric property of the obtained electric copper clad laminate is better along with the increase of the addition of the BVPE compound, so that the increase of the solubility of the BVPE in the resin composition is beneficial to improving the dielectric property of the obtained electric copper clad laminate.
In summary, when the BVPE compound and the resin composition with the BVPE compound are applied to prepregs, electric copper-clad plates and circuit boards, the BVPE compound can provide excellent dielectric properties, heat resistance, thermal decomposition temperature and peeling strength for the prepregs, the electric copper-clad plates and the circuit boards, so that the prepregs, the electric copper-clad plates and the circuit boards containing the resin composition have excellent dielectric properties, heat resistance, thermal decomposition temperature and peeling strength, and are beneficial to the wide application of the prepregs, the electric copper-clad plates and the circuit boards in the field of high-frequency high-speed electronics.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present application, and not for limiting the same; although the application has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features can be replaced equivalently; such modifications and substitutions do not depart from the spirit of the application.
Claims (23)
1. The resin composition is characterized by comprising the following components in parts by weight:
10 to 30 parts of BVPE compound
40-80 Parts of polyphenyl ether resin
Initiator 0.01-3 parts
Wherein the BVPE compound is selected from one or more of modified BVPE polymers;
The modified BVPE polymer is an oligomer, and a modified compound adopted by the modified BVPE polymer is a substituted or unsubstituted benzoxazine resin containing vinyl; introducing a modified compound by double bond initiation in the modification process to obtain a BVPE oligomer;
The chemical structural formula of the polyphenyl ether resin is shown as a formula X:
Wherein X is any one of methylene, oxygen atom, carbonyl and isopropyl;
u and v are independently selected from natural numbers of 1-10.
2. The resin composition according to claim 1, wherein the benzoxazine in the substituted vinyl-containing benzoxazine resin is selected from any one of a mono-benzoxazine ring or a bis-benzoxazine ring.
3. The resin composition according to claim 2, wherein the benzoxazine is one or more selected from the group consisting of bisphenol A type benzoxazine, bisphenol F type benzoxazine, phenolphthalein type benzoxazine, dicyclopentadiene type benzoxazine, and phosphorus-containing DOPO type benzoxazine.
4. A resin composition according to claim 3, wherein the benzoxazine has a chemical formula selected from the group consisting of:
Any one of them;
Wherein R 1、R3 is independently selected from Any one of phenyl, x=0 or 1; r 2 is selected from any one of H, alkyl containing 1-6 carbon atoms, phenyl, epoxy, amino and nitro; r 4 is selected from any one of phenyl and nitrobenzene; r 5 is any one of methoxy; r 6 is selected from any one of methylene, isopropyl, oxygen atom and carbonyl; r 7 is selected from any one of hydrogen and allyl; r 8 is selected from any one of methylene, oxygen atom and the like.
5. The resin composition according to claim 2, wherein the modified BVPE polymer is selected from one or more of the compounds of the chemical structural formulae V to VII; the chemical structural formula of the compound shown in the formulas V-VII is shown as follows:、
、
wherein j, k and p are independently selected from natural numbers of 1-10;
Wherein R 1、R3 is independently selected from Any one of phenyl, h=0 or 1; r 2 is selected from any one of H, alkyl containing 1-6 carbon atoms, phenyl, epoxy, amino and nitro; r 5 is any one of methoxy; r 6 is selected from any one of methylene, isopropyl, oxygen atom and carbonyl; r 7 is selected from any one of hydrogen and allyl; r 8 is selected from any one of methylene, oxygen atom and the like.
6. The resin composition according to claim 1, wherein the initiator is an initiator that promotes radical polymerization of carbon-carbon unsaturated bonds and double bonds at 130 to 180 ℃.
7. The resin composition of claim 1, wherein the initiator is selected from one or more of peroxides.
8. The resin composition according to claim 7, wherein the peroxide is any one selected from the group consisting of di-t-butyl peroxide, t-butyl hydroperoxide, and cumene hydroperoxide.
9. The resin composition according to claim 1, further comprising 10 to 50 parts by mass of a filler; and/or;
the resin composition further comprises 30-200 parts by mass of a first solvent.
10. The resin composition according to claim 9, wherein the filler is an organic filler and/or an inorganic filler.
11. The resin composition according to claim 10, wherein the organic filler is one or more selected from polytetrafluoroethylene powder and polyphenylene sulfide; and/or
The inorganic filler is selected from one or more of silicon dioxide, aluminum hydroxide, aluminum oxide and boron nitride.
12. The resin composition according to claim 9, wherein the first solvent is selected from one or more of methanol, ethanol, ethylene glycol monomethyl ether, acetone, butanone, dimethylformamide, dimethylacetamide, methyl isobutyl ketone, methoxyacetone, toluene, cyclohexanone, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, xylene.
13. A method of preparing a resin composition system comprising:
Providing the components of the resin composition according to any one of claims 9 to 12;
Mixing BVPE compound, polyphenyl ether resin, solvent and/or filler;
and adding an initiator, and dispersing to obtain a resin composition system.
14. A prepreg is characterized in that the prepreg comprises attachments,
The deposit is obtained by curing the resin composition according to any one of claims 1 to 12.
15. The prepreg of claim 14, wherein the prepreg further comprises a reinforcing material;
the attachment adheres to the reinforcing material.
16. The prepreg of claim 15, wherein the reinforcing material is selected from at least one of natural fibers, organic synthetic fibers, organic fabrics, and inorganic fabrics.
17. A method for preparing a prepreg, comprising:
Providing a reinforcing material and the resin composition of any one of claims 1 to 12 or providing a reinforcing material and the resin composition system prepared by the method of preparing a resin composition system of claim 13;
And (3) adhering components in the resin composition or the resin composition system to the surface of the reinforcing material, and semi-curing to obtain the prepreg.
18. The method of preparing a prepreg according to claim 17, wherein adhering the components of the resin composition or the resin composition system to the surface of the reinforcing material comprises:
impregnating the reinforcing material with the resin composition or the resin composition system for 0.5-1min.
19. The method for preparing a prepreg according to claim 17, wherein the prepreg comprises:
Heat treating the reinforcing material with the components of the resin composition or the resin composition system attached thereto at 100-200 ℃ for 1-10min.
20. An electrical copper-clad plate, characterized in that it comprises a prepreg obtained by the method for preparing a prepreg according to any one of claims 17 to 19.
21. The electrical copper-clad plate of claim 20 further comprising a copper foil;
the copper foil is coated on one side or both sides of the prepreg.
22. The preparation method of the electric copper-clad plate is characterized by comprising the following steps of:
Providing a copper foil and a prepreg obtained by the method for preparing a prepreg according to any one of claims 17 to 19;
the copper foil is repeated on one side or two sides of the prepreg to obtain a semi-finished device;
pressing the semi-finished product device for 5-10 hours by using a pressing process to obtain the electric copper-clad plate;
the lamination process comprises a first lamination section and a second lamination section; the first pressing section comprises the steps of heating to 170-190 ℃ at a heating rate of 4-6 ℃/min, heating to 5MPa at a heating rate of 0.05-0.2MPa/min, and pressing the semi-finished device for 2-4 h;
the second lamination section includes: and pressing the semi-finished device passing through the first pressing section at 200-240 ℃ and 5MPa for 3-6 h.
23. Use of the resin composition according to any one of claims 1 to 12 or the resin composition system according to claim 13, the prepreg according to any one of claims 14 to 16 or the prepreg according to any one of claims 17 to 19, the electrical copper-clad plate according to any one of claims 20 to 21 or the electrical copper-clad plate according to any one of claims 22 in the field of circuit board manufacturing.
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| WO2024018945A1 (en) * | 2022-07-20 | 2024-01-25 | パナソニックＩｐマネジメント株式会社 | Resin composition, prepreg, film with resin, metal foil with resin, metal-clad laminate, and wiring board |
| CN115612246A (en) * | 2022-12-15 | 2023-01-17 | 成都科宜高分子科技有限公司 | Composition for forming PCB (printed Circuit Board) hole plugging resin, preparation method, application and filling process |
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| CN111116814A (en) * | 2018-10-31 | 2020-05-08 | 台光电子材料(昆山)有限公司 | Prepolymer, method of making, resin composition, and articles thereof |
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| CN112210210B (en) * | 2019-07-11 | 2023-04-25 | 台光电子材料(昆山)有限公司 | Resin composition and product thereof |
| TWI710599B (en) * | 2019-10-14 | 2020-11-21 | 台光電子材料股份有限公司 | Resin composition and its products |
| CN114196189B (en) * | 2021-11-25 | 2024-03-15 | 南亚新材料科技股份有限公司 | Composition suitable for high-heat-oxidation-resistance low-dielectric halogen-free copper foil clad plate and application thereof |
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