CN114292493B - Resin composition and use thereof - Google Patents
Resin composition and use thereof Download PDFInfo
- Publication number
- CN114292493B CN114292493B CN202111661579.2A CN202111661579A CN114292493B CN 114292493 B CN114292493 B CN 114292493B CN 202111661579 A CN202111661579 A CN 202111661579A CN 114292493 B CN114292493 B CN 114292493B
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- CN
- China
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- resin
- epoxy resin
- resin composition
- curing agent
- dicyandiamide
- Prior art date
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- 239000011342 resin composition Substances 0.000 title claims abstract description 56
- 239000003822 epoxy resin Substances 0.000 claims abstract description 59
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 59
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 42
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims abstract description 37
- 229920005989 resin Polymers 0.000 claims abstract description 28
- 239000011347 resin Substances 0.000 claims abstract description 28
- 150000003839 salts Chemical class 0.000 claims abstract description 24
- 239000004593 Epoxy Substances 0.000 claims abstract description 14
- SGUVLZREKBPKCE-UHFFFAOYSA-N 1,5-diazabicyclo[4.3.0]-non-5-ene Chemical compound C1CCN=C2CCCN21 SGUVLZREKBPKCE-UHFFFAOYSA-N 0.000 claims abstract description 13
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 12
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 10
- 239000011574 phosphorus Substances 0.000 claims description 10
- 229910052698 phosphorus Inorganic materials 0.000 claims description 10
- IISBACLAFKSPIT-UHFFFAOYSA-N Bisphenol A Natural products C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 9
- 239000005011 phenolic resin Substances 0.000 claims description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- 229920001568 phenolic resin Polymers 0.000 claims description 7
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 6
- 239000004305 biphenyl Substances 0.000 claims description 6
- 235000010290 biphenyl Nutrition 0.000 claims description 6
- 239000004841 bisphenol A epoxy resin Substances 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical compound C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 abstract description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 5
- 239000001257 hydrogen Substances 0.000 abstract description 5
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 abstract description 3
- 239000003292 glue Substances 0.000 description 30
- -1 allyl modified bismaleimide Chemical class 0.000 description 17
- 239000010410 layer Substances 0.000 description 14
- 239000000843 powder Substances 0.000 description 13
- 230000001070 adhesive effect Effects 0.000 description 12
- 239000004642 Polyimide Substances 0.000 description 11
- 239000000853 adhesive Substances 0.000 description 11
- 239000000945 filler Substances 0.000 description 11
- 229920001721 polyimide Polymers 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 10
- 239000010408 film 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
- 239000003063 flame retardant Substances 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 229920000428 triblock copolymer Polymers 0.000 description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 229920000459 Nitrile rubber Polymers 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000004744 fabric Substances 0.000 description 6
- 239000004843 novolac epoxy resin Substances 0.000 description 6
- 239000004925 Acrylic resin Substances 0.000 description 5
- 229930185605 Bisphenol Natural products 0.000 description 5
- 239000004842 bisphenol F epoxy resin Substances 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 229920001971 elastomer Polymers 0.000 description 5
- 238000007306 functionalization reaction Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000005060 rubber Substances 0.000 description 5
- 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 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- INKDAKMSOSCDGL-UHFFFAOYSA-N [O].OC1=CC=CC=C1 Chemical compound [O].OC1=CC=CC=C1 INKDAKMSOSCDGL-UHFFFAOYSA-N 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
- 229910052796 boron Inorganic materials 0.000 description 4
- 239000011889 copper foil Substances 0.000 description 4
- 239000003365 glass fiber Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- 239000012779 reinforcing material Substances 0.000 description 4
- 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
- 125000005396 acrylic acid ester group Chemical group 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- 230000008646 thermal stress 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
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-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
- 238000004026 adhesive bonding Methods 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
- 150000001412 amines Chemical class 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
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229910021538 borax Inorganic materials 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
- 239000011258 core-shell material Substances 0.000 description 2
- 239000013039 cover film Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 239000012796 inorganic flame retardant Substances 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229920000058 polyacrylate Polymers 0.000 description 2
- 229920000193 polymethacrylate Polymers 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000004080 punching Methods 0.000 description 2
- 239000004328 sodium tetraborate Substances 0.000 description 2
- 235000010339 sodium tetraborate Nutrition 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000010959 steel Substances 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
- 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
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- QIRNGVVZBINFMX-UHFFFAOYSA-N 2-allylphenol Chemical compound OC1=CC=CC=C1CC=C QIRNGVVZBINFMX-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
- 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
- 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
- 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
- 125000002723 alicyclic 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
- 230000000740 bleeding effect Effects 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 239000002981 blocking agent Substances 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
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 229910002026 crystalline silica Inorganic materials 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000011152 fibreglass Substances 0.000 description 1
- 239000005350 fused silica glass 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
- 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
- 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
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000000465 moulding Methods 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
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 229950000688 phenothiazine Drugs 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920001485 poly(butyl acrylate) polymer Polymers 0.000 description 1
- 229920001490 poly(butyl methacrylate) polymer Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920000120 polyethyl acrylate Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920013636 polyphenyl ether polymer Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 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
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 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
- 229920001187 thermosetting polymer Polymers 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
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 210000000707 wrist Anatomy 0.000 description 1
Landscapes
- Reinforced Plastic Materials (AREA)
Abstract
The present invention provides a resin composition and application thereof, the resin composition comprising: epoxy resin: 100 parts by weight; dicyandiamide, wherein the ratio of the active hydrogen equivalent of dicyandiamide to the epoxy equivalent of the epoxy resin is 0.5-2.0; co-curing agent: as the co-curing agent of dicyandiamide, the co-curing agent is selected from one or a combination of any several of 1,8 diazabicyclo (5, 4, 0) -7-undecene and salts thereof, 1,5 diazabicyclo (4, 3, 0) non-5-ene and salts thereof, the addition amount of the co-curing agent is 0.15-1.0 by weight ratio of the co-curing agent to dicyandiamide; and the weight ratio of the weight of the ductile resin to the total weight of the epoxy resin, the cyanamide and the co-curing agent is 0.01-0.5 by weight.
Description
Technical Field
The invention relates to the technical field of electronic materials, in particular to a resin composition and application thereof.
Background
Currently, a rigid-flex printed circuit board is a printed circuit board which is currently in great demand and development. The rigid-flex printed circuit board is formed by combining a lamellar flexible bottom layer and a rigid bottom layer and laminating the lamellar flexible bottom layer and the rigid bottom layer into a single component, the rigid-flex printed circuit board changes the traditional planar design concept, expands to a three-dimensional 3-dimensional space concept, and brings great convenience to product design and also brings great challenges. A typical (four layer) flex-rigid printed circuit board has a polyimide core with copper foil on both its upper and lower surfaces. The outer rigid layer consists of single sided FR4 (fiberglass board) laminated to both sides of the flexible core, assembled into a multi-layer PCB. In the fabrication of a multi-layer flex-rigid board, the flex layer is processed by a process that is distinct from the external FR4 layer. The layers of different materials must be gathered together by lamination, then drilled and electroplated. Thus, a typical four-layer flex-rigid printed circuit board may be fabricated 5 to 7 times longer than a standard four-layer flex-rigid printed circuit board. At present, the application range of the rigid-flex printed circuit board mainly comprises: aerospace, such as high-end aircraft mounted weapon navigation systems, advanced medical devices, digital cameras, portable cameras 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 great benefits to the design of a military aircraft because it reduces weight while improving connection reliability.
The rigid-flex printed circuit board needs to be bonded with a soft board and a hard board by using a bonding material when in processing and manufacturing, and the most common bonding material in the prior art is a low-fluidity prepreg. Compared with the conventional FR-4 prepreg, the low resin fluidity prepreg needs to have the characteristic of little or no gummosis under high temperature and high pressure, and also needs to have good adhesive force, excellent toughness and low powder falling property. Because of the minimal or little bleeding of low-flow prepregs at high temperatures and pressures, it is often desirable to increase the degree of reaction of the resin system, which can result in a reduction in the bonding ability of the adhesive sheet. Particularly, the bonding force between the low-flow glue prepreg and the polyimide surface of the soft board is one of factors which seriously influence the reliability of the soft and hard combined board. In addition, with the increase of product requirements, a higher proportion of filler needs to be added into the low-flow glue prepreg in some cases, which also leads to the obvious decrease of the bonding force between the low-flow glue prepreg and the polyimide surface of the flexible board.
In order to solve the problem of the bonding force between the low-flow prepreg and the polyimide surface of the flexible board, the thermosetting resin composition composed of allyl modified bismaleimide resin and epoxy resin with a special structure is used in the Chinese patent application CN104164087A, and the problem of the bonding force between the low-flow prepreg and the polyimide surface of the flexible board is mainly solved by using the epoxy resin with the special structure in the patent. However, the technical proposal in the patent has the problem of large powder dropping caused by insufficient toughness, and can seriously affect the processing performance of the printed circuit board. To improve the toughness problem of the low-flow prepregs, too much bisphenol a type epoxy resin is added, which in turn causes the problem of lower glass transition temperature.
In order to improve toughness and powder dropping performance of the low-flow prepreg, in the prior art, macromolecular polymers such as phenol-oxygen resin, nitrile rubber, polyacrylate resin and the like are generally added into a resin system, however, excessive addition of macromolecular polymers can cause the wettability of the resin system to glass fiber cloth to be reduced, and defects such as resin cavities are formed in the prepreg, which can cause the reliability to be reduced after the low-flow prepreg is pressed.
Therefore, a novel resin composition and a low-flow glue prepreg manufactured by using the same are developed, the bonding force between the low-flow glue prepreg and the polyimide surface of a soft board is improved, the low-flow glue prepreg is ensured to have excellent heat resistance, toughness and low powder dropping property, the problem of reduced wettability of a resin system to glass fiber cloth can be avoided, and the low-flow glue prepreg has positive practical significance obviously.
Disclosure of Invention
The invention solves the problem of providing a resin composition and application thereof, wherein the resin composition is applied to a low-gummosis prepreg, has low gummosis quantity and excellent adhesive force, and particularly has excellent adhesive force between the low-gummosis prepreg and a polyimide surface of a flexible board in the application of a printed circuit board substrate (laminated board) of a rigid-flex printed circuit board.
In order to solve the above problems, the present invention provides a resin composition comprising:
Epoxy resin: 100 parts by weight;
Dicyandiamide, wherein the ratio of the active hydrogen equivalent of dicyandiamide to the epoxy equivalent of the epoxy resin is 0.5-2.0;
Co-curing agent: as the co-curing agent of dicyandiamide, the co-curing agent is selected from one or a combination of any several of 1,8 diazabicyclo (5, 4, 0) -7-undecene and salts thereof, 1,5 diazabicyclo (4, 3, 0) non-5-ene and salts thereof, the addition amount of the co-curing agent is 0.15-1.0 by weight ratio of the co-curing agent to dicyandiamide; and
The weight ratio of the weight of the ductile resin to the total weight of the epoxy resin, the cyanamide and the co-curing agent is 0.01-0.5 by weight.
As an alternative technical scheme, the weight ratio of the co-curing agent to the dicyandiamide is 0.3-1.0.
As an alternative technical scheme, the ratio of the active hydrogen equivalent of the dicyandiamide to the epoxy equivalent of the epoxy resin is 0.5 to 1.0
As an optional technical solution, the method further includes: and a boron-containing compound in a weight ratio of 0.1 to 2.0 to the co-curing agent.
Alternatively, the boron-containing compound is selected from boric acid or borax.
As an alternative technical scheme, the epoxy resin is selected from one or more of DOPO-HQ modified epoxy resin, biphenyl type epoxy resin, bisphenol type phenolic epoxy resin, bisphenol A-containing epoxy resin, bisphenol F epoxy resin, dihydroxydiphenyl ether epoxy resin and allyl glycidyl ether.
As an alternative technical scheme, the salt of 1,8 diazabicyclo (5, 4, 0) -7-undecene is a salt of 1,8 diazabicyclo (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 alternative technical scheme, the ductile resin can be selected from one or more of phenol-oxygen resin, nitrile rubber, core-shell rubber and polyacrylate resin.
The invention also provides application of the resin composition to low-flow glue prepregs.
The invention also provides application of the low-flow glue prepreg, which is applied to a laminated board.
In conclusion, the resin composition and the application thereof, and the dicyandiamide and dicyandiamide co-curing agent system can obviously improve the PI film bonding strength of the low-flow glue prepreg prepared based on the resin composition, and simultaneously have excellent heat resistance, bonding performance, lower powder removal rate and lower glue overflow amount.
Compared with the prior art, the invention develops a resin composition and application thereof, and has the following beneficial effects:
in the resin composition for preparing the low-gumming prepreg, the amine curing agent and the co-curing agent with a special structure are creatively combined to obtain the low-gumming bonding sheet with excellent heat resistance, bonding performance, lower powder removal rate and lower gum overflow amount, and particularly, the bonding force between the low-gumming bonding sheet and the polyimide surface of the soft board is remarkably improved.
The present invention will be described in detail with reference to specific examples, but is not limited thereto.
Detailed Description
The present invention will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
The invention aims to provide a resin composition and application thereof, wherein dicyandiamide curing agent is used in the resin composition, and any one or more of 1,8 diazabicyclo (5, 4, 0) -7-undecene (DBU) and salts thereof, and 1,5 diazabicyclo (4, 3, 0) non-5-ene (DBN) and salts thereof are used as co-curing agents of dicyandiamide, so that the cured product formed based on the resin composition has excellent heat resistance, bonding performance, lower powder removal rate and lower glue overflow amount, and particularly the bonding force between a bonding sheet and a polyimide surface of a flexible board is remarkably improved by the formed low-glue-flow semi-curing.
Specifically, the present invention provides a resin composition comprising:
Epoxy resin: 100 parts by weight;
Dicyandiamide, wherein the ratio of the active hydrogen equivalent of dicyandiamide to the epoxy equivalent of the epoxy resin is 0.5-2.0;
Co-curing agent: as the co-curing agent of dicyandiamide, the co-curing agent is selected from any one or more of 1,8 diazabicyclo (5, 4, 0) -7-undecene and salts thereof, 1,5 diazabicyclo (4, 3, 0) non-5-ene and salts thereof, the addition amount of the co-curing agent is 0.15-1.0 by weight ratio of the co-curing agent to dicyandiamide; and
The weight ratio of the weight of the ductile resin to the total weight of the epoxy resin, the cyanamide and the co-curing agent is 0.01-0.5 by weight.
Wherein the ratio of the active hydrogen equivalent of dicyandiamide to the epoxy equivalent of the epoxy resin is preferably 0.5 to 1.0
Preferably, the weight ratio of co-curing agent to dicyandiamide is 0.3-1.0 by weight.
In the above technical scheme, the epoxy resin refers to a generic term of a polymer containing more than two epoxy groups in a molecule. The epoxy resin can be selected from one or more of 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 type epoxy resin, dicyclopentadiene type epoxy resin, isocyanate type epoxy resin, phenolic epoxy resin, methyl phenolic epoxy resin, bisphenol type phenolic epoxy resin, polyphenyl ether modified epoxy resin, alicyclic epoxy resin, allyl glycidyl type epoxy resin, glycidyl amine type epoxy resin and glycidyl ester type epoxy resin.
In order to ensure that the obtained low-flow prepreg and the soft board polyimide have good surface binding force, the epoxy resin preferably contains one or more of DOPO-HQ type phosphorus-containing epoxy resin, biphenyl type epoxy resin and bisphenol type phenolic epoxy resin; more preferably, the epoxy resin comprises bisphenol type novolac epoxy resin, and the bisphenol type novolac epoxy resin may be bisphenol a type novolac epoxy resin, bisphenol F type novolac epoxy resin, bisphenol S type novolac epoxy resin, or dihydroxydiphenyl ether type novolac epoxy resin.
In order to make the resin system in the obtained low-flow prepreg have good wettability to glass fiber cloth and avoid the defects of forming resin holes and the like in the prepreg, the epoxy resin preferably contains one or more small molecule epoxy resins such as bisphenol A epoxy resin, bisphenol F epoxy resin, dihydroxydiphenyl ether epoxy resin, allyl glycidyl ether, N, N, N ', N ' -tetraepoxypropyl-4, 4' -diaminodiphenyl methane and the like.
Preferably, in order to provide the obtained low-flow adhesive sheet with better anti-sticking property and heat resistance, when one or more of bisphenol a epoxy resin, bisphenol F epoxy resin, dihydroxydiphenyl ether epoxy resin, and allyl glycidyl ether is contained in the epoxy resin, the total amount of one or more of bisphenol a epoxy resin, bisphenol F epoxy resin, dihydroxydiphenyl ether epoxy resin, and allyl glycidyl ether added is 1 to 15wt% of the total solid content of the resin composition.
In the above technical scheme, the dicyandiamide co-curing agent is one or any one selected from 1,8 diazabicyclo (5, 4, 0) -7-undecene (DBU) and salts thereof, and 1,5 diazabicyclo (4, 3, 0) non-5-ene (DBN) and salts thereof.
Among them, salts of 1,8 diazabicyclo (5, 4, 0) -7-undecene (abbreviated to DBU) are exemplified by those available from San-Apro corporation under the product name ：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 and the like, and salts of 1,8 diazabicyclo (5, 4, 0) -7-undecene (DBU); salts of 1,5 diazabicyclo (4, 3, 0) non-5-ene (abbreviated as DBN) may be exemplified as those available from: san-Apro Co., product name: salts of 1,5 diazabicyclo (4, 3, 0) non-5-ene (DBN) such as U-CAT SA881, U-CAT SA891, and the like.
Further, in the above-mentioned technical scheme, the salt of 1,8 diazabicyclo (5, 4, 0) -7-undecene (DBU) is preferably a salt of 1,8 diazabicyclo (5, 4, 0) -7-undecene (DBU) and a phenolic resin; salts of 1,5 diazabicyclo (4, 3, 0) non-5-ene (DBN) are preferably salts of 1,5 diazabicyclo (4, 3, 0) non-5-ene (DBN) and phenolic resins.
In addition, from the viewpoint of formulation process operability and storage stability, boron-containing compounds such as boric acid and borax may be added to the formulation in an amount such that the weight ratio of the boron-containing compound to the co-curing agent is 0.1 to 2.0 to slow down the curing reaction. Other similar chemicals that slow down the reaction of the curing agent may also be added.
In the technical scheme, the tough resin can be one or more selected from phenol-oxygen resin, nitrile rubber, core-shell rubber and polyacrylate resin.
The phenol oxygen resin can be selected from one or more of allyl phenol oxygen resin, phosphorus-containing phenol oxygen resin, sulfur-containing phenol oxygen resin, bisphenol A glycidyl ether type, bisphenol F glycidyl ether type or biphenyl type glycidyl ether type phenol oxygen resin; preferably, the weight average molecular weight is 5000-70000; more preferably, the weight average molecular weight thereof is 20000 to 50000.
The nitrile rubber may be selected from carboxylated nitrile rubber, aminonitrile rubber or other modified nitrile rubber, preferably a solid rubber or modified solid rubber of relatively high molecular weight, more preferably having a weight average molecular weight of 50000 to 300000.
The polyacrylate resin may be selected from acrylate homopolymers, other vinyl monomers, and copolymers of acrylate. Preferably, the polyacrylate is an acrylate triblock copolymer. The acrylate triblock copolymer refers to a triblock copolymer comprising a middle flexible segment and hard segments at both ends. The middle flexible block can be a block with good flexibility such as polybutyl acrylate, polybutyl methacrylate, polyethyl acrylate, isooctyl polyacrylate, poly (2-ethylhexyl) acrylate, poly (2-ethylhexyl) methacrylate or polybutadiene; the hard segments at both ends may be blocks with better rigidity such as polymethacrylate and polystyrene. Preferably, the acrylate triblock copolymer is a polystyrene-polybutadiene-polymethacrylate triblock copolymer, a polymethyl methacrylate-polybutyl acrylate-polymethyl methacrylate triblock copolymer. Preferably, the weight average molecular weight of the acrylate triblock copolymer is 10000 to 800000, more preferably, the weight average molecular weight of the acrylate triblock copolymer is 10000 to 300000. When the molecular weight is large, the toughness and heat resistance of the acrylic ester are good, but there may be a problem of compatibility with other resins. In order to improve the compatibility of the acrylic ester and other resins, the acrylic ester block copolymer may be modified by functionalization, and may be modified by hydroxyl functionalization, carboxyl functionalization, amino functionalization, or epoxy functionalization. The amount of the polyacrylate resin to be 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 acrylic acid ester is high, the addition amount of the acrylic acid ester may be appropriately reduced in order to improve the compatibility of the acrylic acid ester with other resins, and the addition amount is preferably 1 to 5 parts by weight.
The resin composition of the present invention may further include a flame retardant, and the flame retardant may be 5 to 30% by weight based on the total weight of the resin composition. The flame retardant may be a phosphorus flame retardant, a nitrogen flame retardant, a silicone flame retardant, an inorganic flame retardant, or the like. The phosphorus flame retardant may be an organic phosphorus-containing compound such as a phosphorus-containing phenolic resin, an inorganic phosphorus, a phosphate 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, and tris (2, 6-dimethylphenyl) phosphazene. The nitrogen-based flame retardant may be a triazine compound, cyanuric acid compound, isocyanic acid compound, phenothiazine, or the like. The silicone flame retardant may be silicone oil, silicone rubber, silicone resin, or the like. The inorganic flame retardant may be aluminum hydroxide, magnesium hydroxide, aluminum oxide, barium oxide, or the like.
The resin composition of the present invention may further comprise a filler, and the proportion of the filler to the total weight of the resin composition may be 5 to 80% 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 put into or pre-prepared into a filler dispersion or made into a paste to be put into a resin composition. The particle size of the filler is preferably 0.5 to 10 μm (particle size D50).
In order to give the resulting low-flow prepregs excellent drop out, the filler content is preferably: the filler accounts for 5 to 15 percent of the resin composition.
In order to give the resulting low-flow prepreg excellent in rigidity and thermal conductivity, the filler content is preferably 50 to 70%. In order to obtain a low-flow prepreg which has excellent thermal conductivity and also has excellent interlayer adhesion and copper foil adhesion, the filler is preferably alumina.
In addition, the resin composition of the present invention may further contain special functional aids such as dispersants, coupling agents, defoamers, leveling agents, colorants, compatibilizers, UV blocking agents, and the like.
The invention also provides a low-flow glue prepreg prepared by using the resin composition.
The preparation method of the low-gummosis prepreg comprises the following steps:
Adding the resin composition and the solvent into a glue mixing kettle to prepare a reactant with the solid content of 40-70%, uniformly stirring, and curing for 4-8 hours to prepare a resin composition glue solution; then the reinforcing material is immersed in the resin composition glue solution, and the immersed reinforcing material is reacted and dried in the environment of 100-200 ℃ according to the set procedure, thus obtaining the low-gummosis prepreg.
The reinforcing material may be natural fibers, organic synthetic fibers, organic fabrics or inorganic fabrics.
The solvent is one or more of N, N-dimethylformamide, N-dimethylacetamide, acetone, butanone, propylene glycol methyl ether, ethylene glycol ethyl ether, methanol, ethanol, benzene, toluene, paraxylene, tetrahydrofuran, N-methylpyrrolidone and dimethyl sulfoxide.
The preparation process of the resin composition glue solution comprises the following steps:
the components were uniformly mixed and stirred in the amounts shown in Table 1, and cured for 4 to 8 hours to prepare resin composition pastes 1 to 5 having 50% solids content in examples 1 to 5 and resin composition pastes 6 to 9 in comparative examples 1 to 4.
Table 1 resin compositions each component and amount (by weight)
The resin composition glue solutions 1 to 5 in examples 1 to 5 and the resin composition glue solutions 6 to 9 in comparative examples 1 to 4 were used to prepare low-flow prepregs, and the corresponding laminates were prepared using the low-flow prepregs.
The electronic grade 2116 glass fiber cloth is used as a reinforcing material to be impregnated with the resin composition glue solution, then the prepreg is heated and cured in an oven according to a certain temperature and time program to obtain the low-flow glue prepreg, part of the prepreg is pressed into a laminated plate according to the following conditions, and then the properties of the prepreg and the laminated plate are evaluated by the following methods.
Specific manufacturing conditions of the prepreg and the laminated board are as follows:
prepreg curing conditions: temperature: 130-190 ℃; time: 2-10min;
The manufacturing conditions of the plate are as follows: the stacking structure is 1/2OZ Cu+2x2116 bonding sheet+1/2 OZ Cu, the copper foil thickness is 1/2OZ, and the thickness of the plate after molding is as follows: 0.25mm, wherein the curing condition is that the temperature rises 3-5 ℃/min, and the material temperature is 200 ℃/1-2h;
The manufacturing conditions of the PI binding force test board are as follows: the lamination is 1/2OZ Cu+25umPI film+1x2116+1/2 OZ Cu, the curing condition is that the temperature rises 3-5 ℃/min, the temperature is 200 ℃ and the time is 1-2h.
The test items and test conditions were as follows:
< determination of glue overflow amount >: and (3) manufacturing a square sample with the size of 100mm multiplied by 100mm from the PP, punching a 1-inch round hole in the middle position, stacking the PP sample together in a stacking mode of steel plate, copper-clad plate, PP sample, release film, buffer material and steel plate, pressing by using a press with set temperature/pressure/time, and taking out the glue overflow amount of the round hole position of the sample after the pressing is finished so as to evaluate the glue overflow amount under the hot pressing condition.
< Powder removal rate) >, measurement: the falling degree of the resin powder after the prepreg is subjected to punching/shearing treatment is taken as a judgment basis. The specific test method is that 4 prepregs with the size of 10cm x 10cm are taken, weighed and recorded as m1. A gap with the depth of 9cm is cut on one side of the sample by using scissors, 29 cutters are cut, each sample is made into 30 strips with the length of 9cm, and each strip is treated in the same way. The hand-held sample was vibrated up and down 30 times with the wrist as the center, and one back and forth was noted as one vibration. And weighing again after finishing, recording the weight as m2, and calculating the powder removal rate of the prepreg according to (m 1-m 2)/m 1 x 100%.
< PI film adhesive strength > measurement: and simulating the stacking condition of the soft and hard combined plate, pressing the adhesive-free surfaces of the low-flow adhesive bonding sheet and the PI cover film together, and using a universal material testing machine to test the bonding strength between the low-flow adhesive bonding sheet and the PI cover film by 90-degree stripping.
< Determination of glass transition temperature (Tg) >: the test was performed using the DMA method according to the method prescribed by IPC-TM-650.2.4.25.
< Determination of copper foil peel Strength >: the peel strength of the metal cap layer was tested according to the "post thermal stress" experimental conditions in the IPC-TM-650.2.4.8 method.
< Determination of 288 ℃ thermal stress >: measured according to the IPC-TM-650.2.6.8 method.
The product performance test structures in examples 1 to 5 and comparative examples 1 to 4 described above are referred to table 2.
Table 2 Performance test of boards obtained with resin composition glue solutions 1 to 5 in examples 1 to 5 and resin composition glue solutions 6 to 9 in comparative examples 1 to 4
From the test data in table 2 above, it can be seen that:
1) The resin compositions in examples 1 to 5 adopt dicyandiamide and dicyandiamide co-curing agent systems, the weight ratio of the dicyandiamide to the dicyandiamide co-curing agent systems is controlled between 0.18 and 0.72, and the low-flow adhesive sheet prepared from the resin composition glue solution formed by the dicyandiamide and dicyandiamide co-curing agent systems has more excellent PI film adhesive strength compared with the resin composition in comparative example 1 through the single curing agent system of DBN, and simultaneously has better heat resistance, adhesive property, lower powder removal rate and lower glue overflow amount.
2) The weight ratio of dicyandiamide and dicyandiamide co-curing agent used in the resin compositions of comparative examples 2, 4 was 0.14 and 1.5, respectively, wherein the PI film bond strength was significantly reduced when the weight ratio was increased to 1.5 or decreased to 0.14, and the 288 ℃ thermal stress test was smaller; that is, the weight ratio of dicyandiamide to dicyandiamide co-curing agent has a remarkable influence on the PI film adhesive strength, and reasonably optimizing the weight ratio can remarkably improve the PI film adhesive strength of the solid (low-flow prepreg) based on the resin composition;
3) In the resin compositions of examples 1 to 5, the PI film adhesive strength of the solid (low-flow prepreg) based on the resin composition can be remarkably improved by increasing the weight ratio of dicyandiamide to dicyandiamide co-curing agent within a certain threshold value range (0.15 to 1.0).
In conclusion, the resin composition and the application thereof, and the dicyandiamide and dicyandiamide co-curing agent system can obviously improve the PI film bonding strength of the low-flow glue prepreg prepared based on the resin composition, and simultaneously have excellent heat resistance, bonding performance, lower powder removal rate and lower glue overflow amount.
Compared with the prior art, the invention develops a resin composition and application thereof, and has the following beneficial effects:
in the resin composition for preparing the low-gumming prepreg, the amine curing agent and the co-curing agent with a special structure are creatively combined to obtain the low-gumming bonding sheet with excellent heat resistance, bonding performance, lower powder removal rate and lower gum overflow amount, and particularly, the bonding force between the low-gumming bonding sheet and the polyimide surface of the soft board is remarkably improved.
The invention has been described with respect to the above-described embodiments, however, the above-described embodiments are merely examples of practicing the invention. In addition, the technical features described above in the different embodiments of the present invention may be combined with each other as long as they do not collide with each other. It is to be noted that the present invention is capable of other various embodiments and that various changes and modifications can be made herein by one skilled in the art without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (4)
1. A resin composition, characterized in that the resin composition comprises:
Epoxy resin: 70g of phosphorus-containing epoxy resin with the epoxy equivalent of 350g/eq, 10g of bisphenol A phenolic epoxy resin with the epoxy equivalent of 205g/eq, 10g of bisphenol A epoxy resin with the epoxy equivalent of 185g/eq and 10g of biphenyl epoxy resin with the epoxy equivalent of 290 g/eq;
Dicyandiamide, 1.8g;
co-curing agent: 0.6g of a salt of 1,5 diazabicyclo (4, 3, 0) non-5-ene and a phenolic resin;
15g of a tough resin and a phenol resin;
and (3) filling: 140.88g of spherical silica.
2. A resin composition, characterized in that the resin composition comprises:
Epoxy resin: 70g of phosphorus-containing epoxy resin with the epoxy equivalent of 350g/eq, 10g of bisphenol A phenolic epoxy resin with the epoxy equivalent of 205g/eq, 10g of bisphenol A epoxy resin with the epoxy equivalent of 185g/eq and 10g of biphenyl epoxy resin with the epoxy equivalent of 290 g/eq;
Dicyandiamide, 1.8g;
co-curing agent: 1.2g of a salt of 1,5 diazabicyclo (4, 3, 0) non-5-ene and a phenolic resin;
15g of a tough resin and a phenol resin;
and (3) filling: 141.6g of spherical silica.
3. The use of a resin composition according to claim 1 or 2, characterized in that it is applied in a low-flow prepreg.
4. Use of a low-flow prepreg according to claim 3, in a laminate.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPH1149844A (en) * | 1997-08-05 | 1999-02-23 | Sumitomo Bakelite Co Ltd | Resin paste for semiconductor |
| JP2000080150A (en) * | 1998-09-03 | 2000-03-21 | Sumitomo Bakelite Co Ltd | Resin paste for semiconductor |
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| JP2974902B2 (en) * | 1993-12-24 | 1999-11-10 | 住友ベークライト株式会社 | Conductive resin paste |
| JPH10316956A (en) * | 1997-05-21 | 1998-12-02 | Sumitomo Kinzoku Electro Device:Kk | Epoxy adhesive for electronic material free from oozing during curing |
| CN108384236A (en) * | 2018-03-16 | 2018-08-10 | 苏州生益科技有限公司 | A kind of resin combination and the low flow prepreg using its preparation |
| WO2020027257A1 (en) * | 2018-08-03 | 2020-02-06 | Ｊｘｔｇエネルギー株式会社 | Composition for cured resins, cured product of said composition, method for producing said composition, method for producing said cured product, and semiconductor device |
| CN112662356A (en) * | 2020-12-21 | 2021-04-16 | 苏州生益科技有限公司 | Resin composition and low-flow-rate prepreg manufactured by using same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPH1149844A (en) * | 1997-08-05 | 1999-02-23 | Sumitomo Bakelite Co Ltd | Resin paste for semiconductor |
| JP2000080150A (en) * | 1998-09-03 | 2000-03-21 | Sumitomo Bakelite Co Ltd | Resin paste for semiconductor |
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