CN114292494A - Resin composition and use thereof - Google Patents
Resin composition and use thereof Download PDFInfo
- Publication number
- CN114292494A CN114292494A CN202111661593.2A CN202111661593A CN114292494A CN 114292494 A CN114292494 A CN 114292494A CN 202111661593 A CN202111661593 A CN 202111661593A CN 114292494 A CN114292494 A CN 114292494A
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- China
- Prior art keywords
- curing agent
- aromatic amine
- resin composition
- resin
- weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000011342 resin composition Substances 0.000 title claims abstract description 58
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 106
- 150000004982 aromatic amines Chemical class 0.000 claims abstract description 57
- 239000003822 epoxy resin Substances 0.000 claims abstract description 46
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 46
- 150000003839 salts Chemical class 0.000 claims abstract description 33
- 229920005989 resin Polymers 0.000 claims abstract description 18
- 239000011347 resin Substances 0.000 claims abstract description 18
- SGUVLZREKBPKCE-UHFFFAOYSA-N 1,5-diazabicyclo[4.3.0]-non-5-ene Chemical compound C1CCN=C2CCCN21 SGUVLZREKBPKCE-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000004593 Epoxy Substances 0.000 claims abstract description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 7
- 239000001257 hydrogen Substances 0.000 claims abstract description 7
- 239000000945 filler Substances 0.000 claims description 13
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 10
- 239000005011 phenolic resin Substances 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 7
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 6
- 229910052796 boron Inorganic materials 0.000 claims description 6
- 229920001568 phenolic resin Polymers 0.000 claims description 6
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 claims description 5
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 claims description 4
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 claims description 4
- 229920001187 thermosetting polymer Polymers 0.000 abstract description 4
- 239000003292 glue Substances 0.000 description 23
- 239000010410 layer Substances 0.000 description 14
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 11
- -1 allyl modified bismaleimide Chemical class 0.000 description 11
- 239000000843 powder Substances 0.000 description 11
- 239000004642 Polyimide Substances 0.000 description 10
- 239000004843 novolac epoxy resin Substances 0.000 description 10
- 229920001721 polyimide Polymers 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 9
- 239000010408 film Substances 0.000 description 9
- 239000003063 flame retardant Substances 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 8
- 239000000853 adhesive Substances 0.000 description 8
- 230000001070 adhesive effect Effects 0.000 description 8
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 8
- 229910052698 phosphorus Inorganic materials 0.000 description 8
- 239000011574 phosphorus Substances 0.000 description 8
- 229920000428 triblock copolymer Polymers 0.000 description 8
- 229920000459 Nitrile rubber Polymers 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 239000004744 fabric Substances 0.000 description 7
- 229920006287 phenoxy resin Polymers 0.000 description 7
- 239000013034 phenoxy resin Substances 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 6
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 239000010949 copper Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 238000003825 pressing Methods 0.000 description 5
- 239000004925 Acrylic resin Substances 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 229930185605 Bisphenol Natural products 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 238000004026 adhesive bonding Methods 0.000 description 4
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 4
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 4
- 239000004842 bisphenol F epoxy resin Substances 0.000 description 4
- 229920001971 elastomer Polymers 0.000 description 4
- 238000007306 functionalization reaction Methods 0.000 description 4
- 239000003365 glass fiber Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 239000012779 reinforcing material Substances 0.000 description 4
- 239000005060 rubber Substances 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000004305 biphenyl Substances 0.000 description 3
- 235000010290 biphenyl Nutrition 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000011889 copper foil Substances 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 2
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000013039 cover film Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 2
- 230000009977 dual effect Effects 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 239000012796 inorganic flame retardant Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920000193 polymethacrylate Polymers 0.000 description 2
- 238000004080 punching Methods 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 230000008646 thermal stress Effects 0.000 description 2
- KGSFMPRFQVLGTJ-UHFFFAOYSA-N 1,1,2-triphenylethylbenzene Chemical compound C=1C=CC=CC=1C(C=1C=CC=CC=1)(C=1C=CC=CC=1)CC1=CC=CC=C1 KGSFMPRFQVLGTJ-UHFFFAOYSA-N 0.000 description 1
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 1
- 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 1
- BSYJHYLAMMJNRC-UHFFFAOYSA-N 2,4,4-trimethylpentan-2-ol Chemical compound CC(C)(C)CC(C)(C)O BSYJHYLAMMJNRC-UHFFFAOYSA-N 0.000 description 1
- KMRIWYPVRWEWRG-UHFFFAOYSA-N 2-(6-oxobenzo[c][2,1]benzoxaphosphinin-6-yl)benzene-1,4-diol Chemical compound OC1=CC=C(O)C(P2(=O)C3=CC=CC=C3C3=CC=CC=C3O2)=C1 KMRIWYPVRWEWRG-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- UDQLIWBWHVOIIF-UHFFFAOYSA-N 3-phenylbenzene-1,2-diamine Chemical compound NC1=CC=CC(C=2C=CC=CC=2)=C1N UDQLIWBWHVOIIF-UHFFFAOYSA-N 0.000 description 1
- 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
- DGUJJOYLOCXENZ-UHFFFAOYSA-N 4-[2-[4-(oxiran-2-ylmethoxy)phenyl]propan-2-yl]phenol Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C1=CC=C(O)C=C1 DGUJJOYLOCXENZ-UHFFFAOYSA-N 0.000 description 1
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 1
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 description 1
- GXIPHHIBYMWSMN-UHFFFAOYSA-N 6-phenylbenzo[c][2,1]benzoxaphosphinine 6-oxide Chemical compound O1C2=CC=CC=C2C2=CC=CC=C2P1(=O)C1=CC=CC=C1 GXIPHHIBYMWSMN-UHFFFAOYSA-N 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 125000005219 aminonitrile group Chemical group 0.000 description 1
- XLJMAIOERFSOGZ-UHFFFAOYSA-N anhydrous cyanic acid Natural products OC#N XLJMAIOERFSOGZ-UHFFFAOYSA-N 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 239000002981 blocking agent Substances 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 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
- 239000003086 colorant Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 229910002026 crystalline silica Inorganic materials 0.000 description 1
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
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- 230000000694 effects Effects 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000011152 fibreglass Substances 0.000 description 1
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- 230000009477 glass transition Effects 0.000 description 1
- 239000004845 glycidylamine epoxy resin Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 229940018564 m-phenylenediamine Drugs 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
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
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- 239000000178 monomer Substances 0.000 description 1
- GKTNLYAAZKKMTQ-UHFFFAOYSA-N n-[bis(dimethylamino)phosphinimyl]-n-methylmethanamine Chemical compound CN(C)P(=N)(N(C)C)N(C)C GKTNLYAAZKKMTQ-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
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- 238000003860 storage Methods 0.000 description 1
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
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- 238000010998 test method Methods 0.000 description 1
- 238000004154 testing of material Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- AAAQKTZKLRYKHR-UHFFFAOYSA-N triphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
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- 238000005303 weighing Methods 0.000 description 1
- 210000000707 wrist Anatomy 0.000 description 1
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- Reinforced Plastic Materials (AREA)
Abstract
The invention provides a thermosetting resin composition and application thereof, wherein the thermosetting resin composition comprises 100 parts by weight of epoxy resin; the epoxy resin curing agent comprises an aromatic amine curing agent, wherein the ratio of active hydrogen equivalent of the aromatic amine curing agent to epoxy equivalent of the epoxy resin is 0.5-2.0 by weight; a co-curing agent as a co-curing agent of an aromatic amine curing agent, the co-curing agent being selected from the group consisting of 1,8 diazabicyclo-bicyclo (5,4,0) -7-undecene (DBU) and salts thereof, and one or more combinations of 1,5 diazabicyclo (4,3,0) non-5-ene (DBN) and salts thereof, the co-curing agent and the aromatic amine curing agent being present in a weight ratio of 0.05 to 0.35; and the tough resin is added in an amount of 0.01-0.5 by weight based on the total weight of the epoxy resin, the aromatic amine curing agent and the co-curing agent.
Description
Technical Field
The invention relates to the technical field of electronic materials, in particular to a resin composition and application thereof.
Background
At present, a printed circuit board with a rigid-flex printed circuit board is a printed circuit board which is currently in strong demand and development. The printed circuit board of the rigid-flex printed circuit board is formed by combining a thin-layer flexible bottom layer and a rigid bottom layer and then laminating the thin-layer flexible bottom layer and the rigid bottom layer into a single component, and the rigid-flex printed circuit board changes the traditional planar design concept and expands the three-dimensional 3-dimensional space concept, thereby bringing great convenience to product design and simultaneously bringing great challenges. A typical (four-layer) flex-rigid printed circuit board has a polyimide core with copper clad on both the top and bottom surfaces. The outer rigid layer is composed of single-sided FR-4 (epoxy fiberglass cloth substrate) which are laminated to both sides of the flexible core to assemble a multilayer Printed Circuit Board (PCB). The process of fabricating the flex layer is again distinct from the outer FR4 layer in making a multi-layer flex-rigid panel. The individual layers made of different materials must be brought together by lamination and then drilled and plated. Thus, the time to make a typical four-layer rigid-flex printed circuit board may be 5 to 7 times longer than making a standard four-layer rigid printed circuit board. At present, the application range of the rigid-flex printed circuit board mainly comprises: aerospace, such as high-end aircraft weapon navigation systems, advanced medical devices, digital cameras, camcorders and high quality MP3 players. Rigid-flex boards are most commonly used in the manufacture of military aircraft and medical equipment. The rigid-flex board provides a great benefit to the design of military aircraft because it reduces weight while improving connection reliability.
When the printed circuit board with the rigid-flex printed circuit board is processed and manufactured, a bonding material is needed to bond the flexible board and the rigid board, and the most commonly used bonding material at the present stage is a low-flow prepreg. Compared with the conventional FR-4 prepreg, the low-flow prepreg needs to have the characteristic of little or no flow of glue at high temperature and high pressure, and also needs to have good adhesion, excellent toughness and low powder removal rate. Due to the very low flow or almost no flow of the low flow prepreg at high temperatures and pressures, it is often desirable to increase the degree of reaction of the resin system, which results in a decrease in its ability to bond as a bondline. Particularly, the bonding force between the low-flow prepreg and the polyimide surface of the flexible printed circuit board is one of the factors which seriously affect the reliability of the flexible-rigid printed circuit board. In addition, with the increase of product requirements, a higher proportion of filler needs to be added into the low-flow prepreg in some cases, which also leads to the obvious reduction of the bonding force of the low-flow prepreg and the polyimide surface of the soft board.
In order to solve the problem of the bonding force between the low flow rate prepreg and the polyimide surface of the flexible printed circuit board, in chinese patent application CN104164087A, a thermosetting resin composition comprising allyl modified bismaleimide resin and an epoxy resin with a special structure is used. However, the technical solution in the patent has a problem of large powder removal rate due to insufficient toughness, and the processing performance of the printed circuit board is seriously affected. In order to improve the toughness of low flow prepreg, too much bisphenol a type epoxy resin is added, which in turn causes a problem that the glass transition temperature becomes low.
In order to improve the toughness and the powder removal rate of the low-flow-rate prepreg, in the prior art, macromolecular polymers such as phenoxy resin, nitrile rubber, polyacrylate resin and the like are usually added into a resin system, however, excessive addition of the macromolecular polymers can reduce the wettability of the resin system on glass fiber cloth, and resin cavities and other defects are formed inside the prepreg, which can reduce the reliability of the low-flow-rate prepreg after pressing.
Therefore, the development of a novel resin composition and a low-flow-rate prepreg manufactured by using the same can improve the binding force between the low-flow-rate prepreg and the polyimide surface of the soft board, ensure that the low-flow-rate prepreg has excellent heat resistance, toughness and low powder removal rate, avoid the problem of reduced wettability of a resin system to glass fiber cloth, and obviously have positive practical significance.
Disclosure of Invention
The invention aims to provide a resin composition and application thereof, which are applied to a low-flow-glue prepreg, so that the low-flow-glue prepreg has low glue overflow amount and excellent bonding force, and particularly the bonding force between the low-flow-glue prepreg and a soft-plate polyimide surface is very excellent.
In order to solve the above problems, the present invention provides a resin composition comprising:
100 parts by weight of epoxy resin;
the epoxy resin curing agent comprises an aromatic amine curing agent, wherein the ratio of active hydrogen equivalent of the aromatic amine curing agent to epoxy equivalent of the epoxy resin is 0.5-2.0 by weight;
a co-curing agent as a co-curing agent for the aromatic amine curing agent, the co-curing agent being selected from the group consisting of 1,8 diazabicyclo-bicyclo (5,4,0) -7-undecene and salts thereof, and one or more combinations of 1,5 diazabicyclo (4,3,0) non-5-ene and salts thereof, the weight ratio of the co-curing agent to the aromatic amine curing agent being 0.05 to 0.35; and
and the tough resin is added in an amount of 0.01-0.5 by weight based on the total amount of the epoxy resin, the aromatic amine curing agent and the co-curing agent.
As an optional technical scheme, the ratio of the active hydrogen equivalent of the aromatic amine curing agent to the epoxy equivalent of the epoxy resin is 0.5-1.5 by weight.
As an optional technical scheme, the weight ratio of the co-curing agent to the aromatic amine curing agent is 0.05-0.25.
As an optional technical scheme, the weight ratio of the co-curing agent to the aromatic amine curing agent is 0.08-0.25.
As an optional technical scheme, the aromatic amine curing agent is diaminodiphenylmethane, diaminodiphenyl sulfone and diaminodiphenyl ether.
As an alternative embodiment, the salt of 1,8 diazabicyclo-bicyclo (5,4,0) -7-undecene is a salt of 1,8 diazabicyclo-bicyclo (5,4,0) -7-undecene and a phenolic resin; the salt of 1,5 diazabicyclo (4,3,0) non-5-ene is a salt of 1,5 diazabicyclo (4,3,0) non-5-ene and a phenolic resin.
As an optional technical solution, the method further comprises: and the filler accounts for 50-70% of the total weight of the resin composition by weight.
As an optional technical solution, the method further comprises: further comprising: a boron-containing compound, wherein the weight ratio of the boron-containing compound to the co-curing agent is 0.1-2.0 by weight.
The resin composition is applied to a low flow prepreg according to the application of the resin composition.
The use of low flow prepregs as described above, in laminates, is described.
In conclusion, the invention provides a resin composition and application thereof, wherein an aromatic amine curing agent and a co-curing agent thereof are adopted in the resin composition, wherein the co-curing agent of aromatic amine is DBN or DBN phenolic resin salt, and DBU or DBU phenolic resin salt, and the weight ratio of the addition amount of the co-curing agent to the aromatic amine curing agent is 0.05-0.35.
Compared with the prior art, the resin composition and the application thereof provided by the invention have the following beneficial effects:
in the resin composition, the aromatic amine curing agent and the co-curing agent (DBN and salt thereof and/or DBU and salt thereof) with a special structure are creatively combined for use, so that the low-flow adhesive bonding sheet which has excellent heat resistance and bonding performance, lower powder removal rate and lower glue overflow amount is obtained, and particularly, the bonding force between the low-flow adhesive prepreg and the soft plate polyimide surface is remarkably improved.
The present invention will be described in detail with reference to specific examples, but the present invention is not limited thereto.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The invention aims to provide a resin composition and application thereof, wherein an aromatic amine curing agent and any one or combination of more of 1,8 diazabicyclo-bicyclo (5,4,0) -7-undecene (DBU) and salt thereof, 1,5 diazabicyclo (4,3,0) non-5-ene (DBN) and salt thereof are used as a co-curing agent of the aromatic amine curing agent in the resin composition, so that a cured product formed based on the resin composition can be effectively improved to have excellent heat resistance, bonding performance, lower powder removal rate and lower glue overflow amount, and particularly, the formed low flow adhesive semi-curing obviously improves the bonding force between a bonding sheet and a soft plate polyimide surface.
Specifically, the invention adopts a technical scheme that the thermosetting resin composition comprises:
100 parts by weight of epoxy resin;
the ratio of active hydrogen equivalent of the aromatic amine curing agent to epoxy equivalent of the epoxy resin is 0.5-2.0;
a co-curing agent as a co-curing agent of an aromatic amine curing agent, the co-curing agent being selected from the group consisting of 1,8 diazabicyclo-bicyclo (5,4,0) -7-undecene (DBU) and salts thereof, and one or more combinations of 1,5 diazabicyclo (4,3,0) non-5-ene (DBN) and salts thereof, the co-curing agent and the aromatic amine curing agent being present in a weight ratio of 0.05 to 0.35;
and the tough resin is added in an amount of 0.01-0.5 by weight based on the total weight of the epoxy resin, the aromatic amine curing agent and the co-curing agent.
Preferably, the ratio of the active hydrogen equivalent of the aromatic amine curing agent to the epoxy equivalent of the epoxy resin is 0.5 to 1.5 by weight.
Preferably, the weight ratio of the co-curing agent to the aromatic amine curing agent is 0.08-0.25.
In the above technical scheme, the component (a), epoxy resin, is a generic name of a polymer containing more than two epoxy groups in a molecule. The epoxy resin can be one or more selected from phosphorus-containing epoxy resin, nitrogen-containing epoxy resin, multifunctional epoxy resin, bisphenol A epoxy resin, bisphenol F epoxy resin, tetraphenylethane epoxy resin, triphenylmethane epoxy resin, biphenyl epoxy resin, naphthalene ring epoxy resin, dicyclopentadiene epoxy resin, isocyanate epoxy resin, novolac epoxy resin, methyl novolac epoxy resin, bisphenol novolac epoxy resin, polyphenyl ether modified epoxy resin, alicyclic epoxy resin, allyl glycidyl epoxy resin, glycidyl amine epoxy resin and glycidyl ester epoxy resin.
In order to ensure that the bonding force between the obtained low-flow-glue prepreg and the polyimide surface of the soft board is good, preferably, the epoxy resin contains one or more of DOPO-HQ type phosphorus-containing epoxy resin, biphenyl type epoxy resin and bisphenol type novolac epoxy resin; more preferably, the epoxy resin comprises bisphenol type novolac epoxy resin, and the bisphenol type novolac epoxy resin can be bisphenol A type novolac epoxy resin, bisphenol F type novolac epoxy resin, bisphenol S type novolac epoxy resin, or dihydroxy diphenyl ether type novolac epoxy resin.
In order to ensure that the resin system in the obtained low-flow-rate prepreg has good wettability to glass fiber cloth and avoid the defects of resin voids and the like formed in the prepreg, the epoxy resin preferably contains one or more of bisphenol A epoxy resin, bisphenol F epoxy resin, dihydroxy diphenyl ether epoxy resin, allyl glycidyl ether, N, N, N ', N ' -tetracyclooxypropyl-4, 4' -diaminodiphenylmethane and other small-molecule epoxy resins.
Preferably, in order to make the obtained low-flow adhesive bonding sheet have better anti-sticking property and heat resistance, when the epoxy resin comprises one or more of bisphenol a epoxy resin, bisphenol F epoxy resin, dihydroxy diphenyl ether epoxy resin and allyl glycidyl ether, the addition amount of the bisphenol a epoxy resin, the bisphenol F epoxy resin, the dihydroxy diphenyl ether epoxy resin and the allyl glycidyl ether is 1-15% of the total solid content of the total resin composition.
In the above technical scheme, the aromatic amine curing agent can be aromatic amine and a modified product thereof.
Examples of the aromatic amine curing agent include m-phenylenediamine and a modified product thereof, diaminodiphenylmethane (DDM) and a modified product thereof, diaminodiphenylsulfone (DDS) and a modified product thereof, diaminodiphenylether and a modified product thereof, m-aminomethane and a modified product thereof, and biphenyldiamine. From the viewpoint of heat resistance, the amine-based curing agent is preferably an aromatic amine-based curing agent, and more preferably diaminodiphenylmethane and a modified product thereof, diaminodiphenylsulfone and a modified product thereof, and diaminodiphenylether and a modified product thereof.
In the above technical scheme, the co-curing agent: the co-curing agent as the aromatic amine curing agent is one or any one selected from 1,8 diazabicyclo-bicyclo (5,4,0) -7-undecene (DBU) and salts thereof, and 1,5 diazabicyclo (4,3,0) non-5-ene (DBN) and salts thereof. The salts of 1,8 diazabicyclo-bicyclo (5,4,0) -7-undecene (DBU) may be enumerated as being available from: salts of 1,8 diazabicyclo-bicyclo (5,4,0) -7-undecene (DBU) from San-Apro company under the product names U-CAT SA1, U-CAT SA102, U-CAT SA603, U-CAT SA810, U-CAT SA506, U-CAT SA831, U-CAT SA841, U-CAT SA851, U-CAT SA838A, etc.; the salts of the 1,5 diazabicyclo (4,3,0) non-5-ene (DBN) may be enumerated as being available from: San-Apro company, under the product name: salts of 1,5 diazabicyclo (4,3,0) non-5-ene (DBN), U-CAT SA881, U-CAT SA891 and the like.
In the above technical scheme, the salt of 1,8 diazabicyclo-bicyclo (5,4,0) -7-undecene (DBU) is preferably a salt of 1,8 diazabicyclo-bicyclo (5,4,0) -7-undecene (DBU) and a phenol resin; the salt of 1,5 diazabicyclo (4,3,0) non-5-ene (DBN) is preferably a salt of 1,5 diazabicyclo (4,3,0) non-5-ene (DBN) and a phenolic resin.
In addition, from the aspects of formula process operability and storage stability, boric acid, borax and other boron-containing compounds can be added into the formula to slow down the curing reaction, and the weight ratio of the boric acid to the co-curing agent is 0.1-2.0. Other similar chemicals that slow the reaction of the curing agent may also be added.
In the above technical scheme, the tough resin may be one or more selected from phenoxy resin, nitrile rubber, core-shell rubber, and polyacrylate resin.
The phenoxy resin can be selected from one or more of allyl phenoxy resin, phosphorus-containing phenoxy resin, sulfur-containing phenoxy resin, bisphenol A glycidyl ether type, bisphenol F glycidyl ether type or biphenyl type glycidyl ether type phenoxy resin; preferably, the weight-average molecular weight is 5000-70000; more preferably, the weight-average molecular weight is 20000 to 50000.
The nitrile rubber can be selected from carboxyl nitrile rubber, amino nitrile rubber or other modified nitrile rubber, preferably solid rubber or modified solid rubber with larger molecular weight, and more preferably, the weight average molecular weight of the nitrile rubber is 50000-300000.
The polyacrylate resin may be selected from the group consisting of acrylate-type homopolymers, copolymers of other vinyl monomers and acrylates. Preferably, the polyacrylate is an acrylate triblock copolymer. The acrylate triblock copolymer refers to a triblock copolymer comprising a middle flexible segment and two hard segments at the two ends. The middle flexible block can be a block with good flexibility, such as polybutyl acrylate, polybutyl methacrylate, polyethyl acrylate, isooctyl acrylate, 2-ethylhexyl methacrylate, polybutadiene, or the like; the hard segments at the two ends can be blocks with better rigidity, such as polymethacrylate, polystyrene and the like. Preferably, the acrylate triblock copolymer is a polystyrene-polybutadiene-polymethacrylate triblock copolymer or a polymethyl methacrylate-polybutyl acrylate-polymethyl methacrylate triblock copolymer. Preferably, the weight average molecular weight of the acrylate triblock copolymer is 10000-800000, and more preferably, the weight average molecular weight of the acrylate triblock copolymer is 10000-300000. When the molecular weight is large, the toughness and heat resistance of the acrylate are good, but there may be a problem of compatibility with other resins. In order to improve the compatibility of the acrylate with other resins, the acrylate block copolymer may be functionally modified, and may be modified by hydroxyl group functionalization, carboxyl group functionalization, amino group functionalization, and epoxy group functionalization. The amount of the polyacrylate resin added is preferably 1 to 10 parts by weight based on 100 parts by weight of the epoxy resin. When the molecular weight of the acrylate is higher, the addition amount of the acrylate can be properly reduced to improve the compatibility of the acrylate with other resins, and the preferable addition amount is 1 to 5 parts by weight.
The resin composition of the present invention may further include a flame retardant, and the flame retardant may account for 5 to 30% by weight of the total weight of the resin composition. The flame retardant may be a phosphorus flame retardant, a nitrogen flame retardant, an organic silicon flame retardant, an inorganic flame retardant, or the like. The phosphorus-containing flame retardant may be an organic phosphorus-containing compound such as a phosphorus-containing phenol resin, inorganic phosphorus, a phosphate ester compound, a phosphonic acid compound, a phosphinic acid compound, a phosphine oxide compound, 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (2, 5-dihydroxyphenyl) -9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-phenyl-9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, tris (2, 6-dimethylphenyl) phosphazene, or the like. The nitrogen-based flame retardant may be a triazine compound, a cyanuric acid compound, an isocyanic acid compound, phenothiazine, or the like. The organic silicon flame retardant can be organic silicon oil, organic silicon rubber, organic silicon resin and the like. The inorganic flame retardant may be aluminum hydroxide, magnesium hydroxide, aluminum oxide, barium oxide, or the like.
The resin composition of the invention may further include a filler, and the filler may account for 5 to 80% of the total weight of the resin composition by weight. The filler can be one or more selected from crystalline silica, fused silica, spherical silica, alumina, aluminum hydroxide, aluminum nitride, boron nitride, titanium dioxide, strontium titanate, barium sulfate, talcum powder, calcium silicate, calcium carbonate, mica, polytetrafluoroethylene and graphene. The filler may be surface-treated with a silane coupling agent, and may be directly charged or may be preliminarily prepared into a filler dispersion or may be charged into a resin composition in the form of a paste. The particle size of the filler is preferably 0.5-10 micrometers (particle size D50).
In order to obtain a low flow prepreg with excellent fraction loss, the filler content is preferably: the filler accounts for 5-15% of the resin composition.
In order to enable the obtained low-flow prepreg to have excellent rigidity and thermal conductivity, the content ratio of the filler is preferably 50-70%. In order to obtain a low flow prepreg having excellent thermal conductivity and excellent interlayer adhesion and copper foil adhesion, the preferred filler is alumina.
In addition, the resin composition of the present invention may further include a special functional auxiliary agent such as a dispersant, a coupling agent, a defoaming agent, a leveling agent, a coloring agent, a compatibilizing agent, a UV blocking agent, and the like.
The invention also provides an application of the resin composition, which is applied to low-flow-rate prepreg.
The preparation method of the low-flow prepreg comprises the following steps: adding the resin composition and a solvent into a glue mixing kettle, uniformly stirring reactants with the solid content of 40-70%, and curing for 4-8 hours to prepare a resin composition glue solution; and then, soaking the reinforcing material in the resin composition glue solution, and then reacting and drying the soaked reinforcing material at the temperature of 100-200 ℃ according to a set program to obtain the low-flow-rate prepreg.
The reinforcing material may be natural fibers, organic synthetic fibers, organic fabrics or inorganic fabrics.
The solvent is one or more selected from N, N-dimethylformamide, N-dimethylacetamide, acetone, butanone, propylene glycol methyl ether, ethylene glycol ethyl ether, methanol, ethanol, benzene, toluene, p-xylene, tetrahydrofuran, N-methylpyrrolidone and dimethyl sulfoxide.
The invention also provides an application of the low-flow-glue prepreg, which is applied to a laminated board.
The specific implementation process of the resin composition glue solution and the low-flow-rate glue prepreg thereof is as follows:
according to the table 1, the components and the solvent were mixed uniformly and cured for 4 to 8 hours to prepare 50% solid content resin composition glue solutions 1 to 7 in examples 1 to 7.
Under the same conditions, the components and the solvent were mixed uniformly and aged for 4 to 8 hours to prepare resin composition glue solutions 8 to 13 having a solid content of 50% in comparative examples 1 to 6.
Using electronic grade 2116 glass fiber cloth as a reinforcing material to impregnate the resin composition glue solutions 1-13, then heating and curing the prepreg in an oven according to a certain temperature and time program to obtain a low-flow-rubber prepreg, pressing part of the prepreg into a laminated board according to the following conditions, and then evaluating the performances of the prepreg and the laminated board by the following methods.
The specific manufacturing process of the low-flow prepreg and the laminated board comprises the following steps:
prepreg (resin composition glues 1 to 13) semi-curing conditions: 130-190 ℃/2-10 min;
the manufacturing conditions of the laminated plate are as follows: the stacking structure is 1/2OZ Cu +2x2116 bonding sheet +1/2OZ Cu, the thickness of the copper foil is 1/2OZ, and the thickness of the formed plate is as follows: 0.25mm, the curing condition is that the temperature rises to 3-5 ℃/min, and the material temperature is 200 ℃/1-2 h;
manufacturing conditions of the PI binding force test plate: the stacking structure is 1/2OZ Cu +25 mu mPI film +1x2116+1/2OZ Cu, the curing condition is that the temperature rises to 3-5 ℃/min, and the material temperature is 200 ℃/1-2 h.
The test items and test conditions for the laminate panels made from the low flow prepreg were as follows:
< measurement of glue overflow >: the method comprises the steps of manufacturing PP into a square sample with the size of 100mm x 100mm, punching a round hole with the size of 1 inch in the middle, then overlapping the PP sample together in a stacking mode of 'steel plate + copper-clad plate + PP sample + release film + buffer material + steel plate', using a press with set temperature/pressure/time for pressing, and taking out the glue overflow amount of the round hole position of the sample after pressing is completed so as to evaluate the glue flowing size of the sample under a hot pressing condition.
< powder removal rate) > measurement: the falling degree of the resin powder after the punching/shearing treatment of the prepreg is taken as a judgment basis. The test was carried out by taking 10cm x 10cm sized pieces of prepreg 4, weighing them and recording them as m 1. A notch with the depth of 9cm is cut on one side of the sample by a pair of scissors, 29 cutters are cut in total, each sample is made into a small strip with the length of 30 strips and the length of 9cm, and each sample is treated in the same way. The hand-held processed sample was vibrated up and down 30 times with the wrist as the center, and one vibration was recorded back and forth as one vibration. After completion, the weight was again measured and recorded as m2, and the powder removal rate of the prepreg was calculated as (m1-m2)/m1 × 100%.
< PI film adhesion strength > measurement: and simulating the stacking condition of the rigid-flex board, pressing the low-flow adhesive sheet and the non-adhesive surface of the PI cover film together, and testing the adhesive strength between the low-flow adhesive sheet and the PI cover film by using a universal material testing machine and 90-degree stripping.
< measurement of copper foil peeling Strength >: the peel strength of the metal cap was tested according to the "post thermal stress" experimental conditions in the IPC-TM-6502.4.8 method.
Determination of thermal stress <288 ℃ >: measured according to the IPC-TM-6502.6.8 method.
The test performance data of the laminate panels measured according to the test methods described above are referred to in table 2.
TABLE 1 Components and amounts of resin compositions in examples 1 to 7 and comparative examples 1 to 6
TABLE 2 Performance testing of Low flow prepregs made from the resin composition dopes of examples 1-7 and comparative examples 1-6
From the performance test data of table 2, it can be seen that:
1) compared with comparative examples 1 and 6, examples 1 to 7 are resin compositions containing an aromatic amine curing agent and an aromatic amine co-curing agent provided by the invention, wherein the weight ratio of the aromatic amine co-curing agent to the aromatic amine curing agent is 0.05 to 0.35, and low-flow adhesive bonding sheets prepared from the resin compositions have more excellent PI film bonding strength, better heat resistance, better bonding performance, lower powder removal rate, lower glue overflow amount and excellent comprehensive performance.
In addition, compared with the co-curing agent system (or dual curing agent system) of 2-ethyl-4-methylimidazole (curing agent) and aromatic amine curing agent in comparative example 6, the co-curing agent of aromatic amine in examples 1 to 7 is DBN or a salt of DBN phenolic resin, and the co-curing agent system (or dual curing agent system) formed by the co-curing agent and the aromatic amine curing agent has a remarkable effect of improving the PI film of the low flow prepreg.
2) Based on the test performance of the low flow prepreg prepared from the resin compositions of examples 3 and 4, it can be seen that the optimal PI film bond strength can be obtained when the weight ratio of the aromatic amine co-curing agent to the aromatic amine curing agent is 0.08, while continuing to reduce the above weight ratio (0.06 and 0.04, 0.048 in comparative examples 3 and 4) has no beneficial effect on the PI film bond strength of the low flow prepreg.
In addition, based on example 5 and comparative examples 2 and 5, it can be seen that the weight ratio of the aromatic amine co-curing agent to the aromatic amine curing agent is greater than 0.35, and the PI film adhesive strength of the low flow prepreg is remarkably reduced.
3) Based on the test performance of the low flow prepreg prepared from the resin composition in example 1 and example 6, it can be seen that the addition of the boron-containing compound helps to stabilize the co-curing agent system of the aromatic amine curing agent and the aromatic amine, and helps to improve the PI film bonding strength of the low flow prepreg positively.
In conclusion, the invention provides a resin composition and application thereof, wherein an aromatic amine curing agent and a co-curing agent thereof are adopted in the resin composition, wherein the co-curing agent of aromatic amine is DBN or DBN phenolic resin salt, and DBU or DBU phenolic resin salt, and the weight ratio of the addition amount of the co-curing agent to the aromatic amine curing agent is 0.05-0.35.
Compared with the prior art, the resin composition and the application thereof provided by the invention have the following beneficial effects:
in the resin composition, the aromatic amine curing agent and the co-curing agent (DBN and salt thereof and/or DBU and salt thereof) with a special structure are creatively combined for use, so that the low-flow adhesive bonding sheet which has excellent heat resistance and bonding performance, lower powder removal rate and lower glue overflow amount is obtained, and particularly, the bonding force between the low-flow adhesive prepreg and the soft plate polyimide surface is remarkably improved.
The present invention has been described in relation to the above embodiments, which are only exemplary of the implementation of the present invention. Furthermore, the technical features mentioned in the different embodiments of the present invention described above may be combined with each other as long as they do not conflict with each other. It is to be noted that the present invention may take various other embodiments, and that various changes and modifications may be effected therein by one skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (10)
1. A resin composition, characterized in that the resin composition comprises:
100 parts by weight of epoxy resin;
the epoxy resin curing agent comprises an aromatic amine curing agent, wherein the ratio of active hydrogen equivalent of the aromatic amine curing agent to epoxy equivalent of the epoxy resin is 0.5-2.0 by weight;
a co-curing agent as a co-curing agent for the aromatic amine curing agent, the co-curing agent being selected from the group consisting of 1,8 diazabicyclo-bicyclo (5,4,0) -7-undecene and salts thereof, and one or more combinations of 1,5 diazabicyclo (4,3,0) non-5-ene and salts thereof, the weight ratio of the co-curing agent to the aromatic amine curing agent being 0.05 to 0.35; and
and the tough resin is added in an amount of 0.01-0.5 by weight based on the total amount of the epoxy resin, the aromatic amine curing agent and the co-curing agent.
2. The resin composition according to claim 1, wherein the ratio of the active hydrogen equivalent of the aromatic amine-based curing agent to the epoxy equivalent of the epoxy resin is 0.5 to 1.5 by weight.
3. The resin composition according to claim 1, wherein the weight ratio of the co-curing agent to the aromatic amine curing agent is 0.05 to 0.25.
4. The resin composition according to claim 3, wherein the weight ratio of the co-curing agent to the aromatic amine curing agent is 0.08 to 0.25.
5. The resin composition according to claim 1, wherein the aromatic amine-based curing agent is at least one of diaminodiphenylmethane, diaminodiphenyl sulfone, and diaminodiphenyl ether.
6. The resin composition according to claim 1,
the salt of 1,8 diazabicyclo-bicyclo (5,4,0) -7-undecene is a salt of 1,8 diazabicyclo-bicyclo (5,4,0) -7-undecene and a phenolic resin;
the salt of 1,5 diazabicyclo (4,3,0) non-5-ene is a salt of 1,5 diazabicyclo (4,3,0) non-5-ene and a phenolic resin.
7. The resin composition according to claim 1, further comprising: and the filler accounts for 50-70% of the total weight of the resin composition by weight.
8. The resin composition according to claim 1, further comprising: further comprising: a boron-containing compound, wherein the weight ratio of the boron-containing compound to the co-curing agent is 0.1-2.0 by weight.
9. Use of a resin composition according to any of claims 1-8 in a low flow prepreg.
10. Use of a low flow prepreg according to claim 9 in laminates.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111661593.2A CN114292494A (en) | 2021-12-31 | 2021-12-31 | Resin composition and use thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN202111661593.2A CN114292494A (en) | 2021-12-31 | 2021-12-31 | Resin composition and use thereof |
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| JP2002053831A (en) * | 2000-08-10 | 2002-02-19 | Mitsui Chemicals Inc | Adhesive resin composition |
| JP2004352939A (en) * | 2003-05-30 | 2004-12-16 | Sumitomo Bakelite Co Ltd | Liquefied encapsulation resin and semiconductor device using it |
| JP2006188573A (en) * | 2005-01-04 | 2006-07-20 | Hitachi Chem Co Ltd | Liquid epoxy resin composition, electronic component device using the composition and method for producing the same |
| JP2006213849A (en) * | 2005-02-04 | 2006-08-17 | Kyocera Chemical Corp | Sealing resin composition and semiconductor sealing apparatus |
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