WO2015154314A1 - Thermoset resin composition - Google Patents
Thermoset resin composition Download PDFInfo
- Publication number
- WO2015154314A1 WO2015154314A1 PCT/CN2014/076014 CN2014076014W WO2015154314A1 WO 2015154314 A1 WO2015154314 A1 WO 2015154314A1 CN 2014076014 W CN2014076014 W CN 2014076014W WO 2015154314 A1 WO2015154314 A1 WO 2015154314A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- resin
- parts
- composition
- solvent
- weight
- Prior art date
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 49
- 239000004634 thermosetting polymer Substances 0.000 title abstract 2
- 229920005989 resin Polymers 0.000 claims abstract description 114
- 239000011347 resin Substances 0.000 claims abstract description 114
- 229920001187 thermosetting polymer Polymers 0.000 claims abstract description 51
- -1 allyl modified bismaleimide Chemical class 0.000 claims abstract description 40
- 239000002904 solvent Substances 0.000 claims abstract description 33
- 239000003822 epoxy resin Substances 0.000 claims abstract description 30
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 30
- 150000002825 nitriles Chemical class 0.000 claims abstract description 25
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 20
- 239000000945 filler Substances 0.000 claims abstract description 7
- 239000011342 resin composition Substances 0.000 claims description 66
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical group O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 claims description 47
- 229920003192 poly(bis maleimide) Polymers 0.000 claims description 37
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 21
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- 229910052751 metal Inorganic materials 0.000 claims description 14
- 239000002184 metal Substances 0.000 claims description 14
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 12
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims description 10
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Natural products C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 9
- 239000012779 reinforcing material Substances 0.000 claims description 9
- 239000000377 silicon dioxide Substances 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- 239000004593 Epoxy Substances 0.000 claims description 8
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 8
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 8
- 239000000347 magnesium hydroxide Substances 0.000 claims description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical group [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 7
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical group NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 6
- 238000012986 modification Methods 0.000 claims description 6
- 230000004048 modification Effects 0.000 claims description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 6
- 229910052698 phosphorus Inorganic materials 0.000 claims description 6
- 239000011574 phosphorus Substances 0.000 claims description 6
- WOCGGVRGNIEDSZ-UHFFFAOYSA-N 4-[2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical compound C=1C=C(O)C(CC=C)=CC=1C(C)(C)C1=CC=C(O)C(CC=C)=C1 WOCGGVRGNIEDSZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000011888 foil Substances 0.000 claims description 5
- 239000011159 matrix material Substances 0.000 claims description 5
- 239000005995 Aluminium silicate Substances 0.000 claims description 4
- 239000004215 Carbon black (E152) Substances 0.000 claims description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 4
- 150000008065 acid anhydrides Chemical class 0.000 claims description 4
- 235000012211 aluminium silicate Nutrition 0.000 claims description 4
- 239000000010 aprotic solvent Substances 0.000 claims description 4
- 150000004982 aromatic amines Chemical class 0.000 claims description 4
- 239000011889 copper foil Substances 0.000 claims description 4
- 229930195733 hydrocarbon Natural products 0.000 claims description 4
- 150000002430 hydrocarbons Chemical class 0.000 claims description 4
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical group COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 claims description 4
- 150000003242 quaternary ammonium salts Chemical group 0.000 claims description 4
- 150000003512 tertiary amines Chemical class 0.000 claims description 4
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical group COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 3
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 3
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims description 3
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims description 3
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 3
- 229960001545 hydrotalcite Drugs 0.000 claims description 3
- 229910001701 hydrotalcite Inorganic materials 0.000 claims description 3
- 150000002576 ketones Chemical class 0.000 claims description 3
- 229920003986 novolac Polymers 0.000 claims description 3
- 229920001568 phenolic resin Polymers 0.000 claims description 3
- 239000005011 phenolic resin Substances 0.000 claims description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 125000003944 tolyl group Chemical group 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims 3
- SUAKHGWARZSWIH-UHFFFAOYSA-N N,N‐diethylformamide Chemical compound CCN(CC)C=O SUAKHGWARZSWIH-UHFFFAOYSA-N 0.000 claims 1
- 239000005456 alcohol based solvent Substances 0.000 claims 1
- 239000003759 ester based solvent Substances 0.000 claims 1
- 239000004210 ether based solvent Substances 0.000 claims 1
- 150000002460 imidazoles Chemical group 0.000 claims 1
- 239000005453 ketone based solvent Substances 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 9
- 238000000034 method Methods 0.000 description 27
- 239000000463 material Substances 0.000 description 17
- 239000004744 fabric Substances 0.000 description 11
- 238000002360 preparation method Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 239000003292 glue Substances 0.000 description 8
- 238000011056 performance test Methods 0.000 description 8
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 7
- 239000003063 flame retardant Substances 0.000 description 7
- 230000009477 glass transition Effects 0.000 description 7
- 229910052736 halogen Inorganic materials 0.000 description 7
- 150000002367 halogens Chemical class 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- 239000002131 composite material Substances 0.000 description 6
- OAKJQQAXSVQMHS-UHFFFAOYSA-N hydrazine group Chemical group NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 229910052802 copper Inorganic materials 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- 238000009472 formulation Methods 0.000 description 5
- 150000003949 imides Chemical group 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-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
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 4
- 239000003365 glass fiber Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 238000013517 stratification Methods 0.000 description 4
- 238000005979 thermal decomposition reaction Methods 0.000 description 4
- 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 3
- 230000002411 adverse Effects 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000010030 laminating Methods 0.000 description 3
- ARYZCSRUUPFYMY-UHFFFAOYSA-N methoxysilane Chemical compound CO[SiH3] ARYZCSRUUPFYMY-UHFFFAOYSA-N 0.000 description 3
- 125000002560 nitrile group Chemical group 0.000 description 3
- 230000035699 permeability Effects 0.000 description 3
- 239000013034 phenoxy resin Substances 0.000 description 3
- 229920006287 phenoxy resin Polymers 0.000 description 3
- 150000004714 phosphonium salts Chemical group 0.000 description 3
- 238000004080 punching Methods 0.000 description 3
- 230000005855 radiation Effects 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- CMLFRMDBDNHMRA-UHFFFAOYSA-N 2h-1,2-benzoxazine Chemical group C1=CC=C2C=CNOC2=C1 CMLFRMDBDNHMRA-UHFFFAOYSA-N 0.000 description 2
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 2
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 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
- 235000010290 biphenyl Nutrition 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 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 2
- 238000009835 boiling Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010292 electrical insulation Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000004745 nonwoven fabric Substances 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000004886 process control Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-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
- IZXIZTKNFFYFOF-UHFFFAOYSA-N 2-Oxazolidone Chemical group O=C1NCCO1 IZXIZTKNFFYFOF-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
- ZYUVGYBAPZYKSA-UHFFFAOYSA-N 5-(3-hydroxybutan-2-yl)-4-methylbenzene-1,3-diol Chemical compound CC(O)C(C)C1=CC(O)=CC(O)=C1C ZYUVGYBAPZYKSA-UHFFFAOYSA-N 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- IBDACVUZZNXEAA-UHFFFAOYSA-N C(C)N(C=O)CC.NN Chemical compound C(C)N(C=O)CC.NN IBDACVUZZNXEAA-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- HECLRDQVFMWTQS-UHFFFAOYSA-N Dicyclopentadiene Chemical compound C1C2C3CC=CC3C1C=C2 HECLRDQVFMWTQS-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 229920010524 Syndiotactic polystyrene Polymers 0.000 description 1
- LEHOTFFKMJEONL-UHFFFAOYSA-N Uric Acid Chemical compound N1C(=O)NC(=O)C2=C1NC(=O)N2 LEHOTFFKMJEONL-UHFFFAOYSA-N 0.000 description 1
- TVWHNULVHGKJHS-UHFFFAOYSA-N Uric acid Natural products N1C(=O)NC(=O)C2NC(=O)NC21 TVWHNULVHGKJHS-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000004842 bisphenol F epoxy resin Substances 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 235000013877 carbamide Nutrition 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- NHADDZMCASKINP-HTRCEHHLSA-N decarboxydihydrocitrinin Natural products C1=C(O)C(C)=C2[C@H](C)[C@@H](C)OCC2=C1O NHADDZMCASKINP-HTRCEHHLSA-N 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 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
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- PYGSKMBEVAICCR-UHFFFAOYSA-N hexa-1,5-diene Chemical group C=CCCC=C PYGSKMBEVAICCR-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 238000012966 insertion method Methods 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- 239000005340 laminated glass Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000006011 modification reaction Methods 0.000 description 1
- OXKUGIFNIUUKAW-UHFFFAOYSA-N n,n-dimethylformamide;hydrazine Chemical compound NN.CN(C)C=O OXKUGIFNIUUKAW-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001955 polyphenylene ether Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000009774 resonance method Methods 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 229940116269 uric acid Drugs 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/04—Layered products comprising a layer of synthetic resin as impregnant, bonding, or embedding substance
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/38—Layered products comprising a layer of synthetic resin comprising epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/12—Unsaturated polyimide precursors
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
Definitions
- the present invention relates to a resin composition, in particular to a thermosetting resin composition and a prepreg and a laminate for the same, which are applicable to the field of electronic materials, and can be applied to integrated circuit packages, high-frequency high-speed and high Density interconnection.
- the electronics industry is developing rapidly due to its multi-functionality, high performance and light weight.
- the initial PTH Insertion method gradually transitioned to the surface mount (SMT) mode, and then evolved to the current BGA, CSP and Flip Chip as the main package form.
- SMT surface mount
- Rapidly evolving technologies place even more stringent requirements on printed circuit boards and copper clad laminates.
- the related products are required to have a series of excellent comprehensive properties such as environmentally friendly flame retardancy, high heat resistance, high heat and humidity resistance, low thermal expansion coefficient, and high elastic modulus.
- Substrate resins widely used in the art include polyphenylene ether, bismaleimide-triazine resin (BT resin), polyimide, and high heat resistant epoxy resin.
- BMI bismaleimide
- maleimide is a kind of bifunctional compound with maleimide as active end group, which has excellent electrical insulation, wave permeability, flame retardancy, heat resistance and radiation resistance. , as well as good mechanical properties and dimensional stability, and have similar fluidity and plasticity to epoxy resin, so the molding process is similar to epoxy resin.
- Bismaleimide has become a very important and most commonly used resin matrix in the synthesis and preparation of high performance composite materials. For example, it can be made into high temperature insulating materials or adhesives, which are widely used in automobile manufacturing, electronic products, machinery. , aerospace and other fields.
- bismaleimide also has many disadvantages, such as: its melting point is 150 ° C, it can only be dissolved in a solvent with strong polarity; its cured product has high brittleness, low impact strength, high curing temperature, etc. Horse Although the benzene ring and the nitrogen element are present in the imide structure, it has a certain flame retardant property, but it cannot meet the requirements of UL-V0 in practical applications.
- the disadvantages of the bismaleimide limit its scope of application and require corresponding modification to meet different needs.
- CN102344567A discloses a preparation method of modified bismaleimide resin, the specific step is to heat mixing amide imide resin and bismaleimide to form a novel modified bismaleimide resin. And mixing the novel modified bismaleimide resin with a thermally conductive powder such as alumina, aluminum nitride, silicon carbide, boron nitride or a mixture thereof to prepare a resin composition, which is applied to a flexible circuit board, Hard circuit boards, integrated circuit packages, liquid crystal display packages or LED packages.
- a thermally conductive powder such as alumina, aluminum nitride, silicon carbide, boron nitride or a mixture thereof
- the method improves the heat resistance of the bismaleimide resin and achieves the purpose of thermosetting, but still does not effectively improve the brittleness of the bismaleimide resin, and the material has a high crosslink density, which is easy to The peel strength of the material adversely affects.
- CN1398274 discloses a halogen-free resin mixture for manufacturing a printed circuit board insulating interlayer, comprising an epoxy resin and a thermosetting maleimide compound, wherein the epoxy resin contains a nitrogen content of 5 ⁇ 25wt% epoxy resin curing agent.
- the resin-free mixture is formed by dissolving the composition in an organic solvent.
- the copper clad laminate prepared by the mixture can achieve excellent comprehensive properties such as halogen-free flame retardant, high heat resistance, excellent water resistance and high peel strength; however, the solution still does not solve the brittleness problem of maleimide, and then
- the epoxy resin itself is also a brittle material, so that the mechanical properties such as impact strength and the drillability of the composite material obtained from the composition are difficult to meet the actual production and application requirements.
- CN101652026 discloses a method for preparing a copper clad plate: firstly mixing and heating a bismaleimide resin and an allyl compound according to a certain weight ratio to prepare a prepolymer, and formulating the prepolymer into a solution; The phosphorus-containing epoxy resin, the composite curing agent and the curing accelerator are added to the prepolymer solution, and the mixture is uniformly stirred to obtain a glue solution, which is pressed into a prepreg to obtain a copper clad laminate.
- the method utilizes an allyl compound to modify the double horse
- the imide resin increases the length of the molecular chain and destroys the regularity of the molecular chain, thereby achieving the purpose of improving the toughness and solubility of the material; and the obtained copper clad plate can meet the requirement of halogen-free flame retardant, and has heat resistance and resistance. Good wet heat, low dielectric loss, and excellent processing toughness.
- phosphorus-containing epoxy resins are used in this scheme, and compatibility with ally-modified bismaleimide resin may cause compatibility problems, and may be resistant to heat resistance of composite materials (such as Tg, resistance). Damp heat performance) adversely affects the implementation of the solution.
- thermosetting resin composition which is required to provide a modified bismaleimide resin and is excellent in guarantee Electrical insulation, wave permeability, flame retardancy, heat resistance, radiation resistance, good mechanical properties and dimensional stability, fluidity and plasticity, providing good toughness, machinability and solvent solubility And has the flame retardancy of UL-V0.
- thermosetting resin composition which has excellent electrical insulating properties, wave permeability, flame retardancy, heat resistance, radiation resistance, and good mechanical properties and dimensional stability. , fluidity and plasticity, and by adjusting the kind and content of each component in the composition, the resin composition not only has good toughness, machinability and solvent solubility, but also can achieve halogen-free flame retardant with UL-V0 Flame retardant.
- Another object of the present invention is to provide a prepreg made of a thermosetting resin composition according to one of the objects of use, which has good machinability, can achieve halogen-free flame retardancy, and has excellent heat and humidity resistance. And heat resistance, low coefficient of thermal expansion, low dielectric constant and dielectric loss.
- a third object of the present invention is to provide a metal foil-clad laminate for a printed circuit made of a thermosetting resin composition according to any one of the above aspects, wherein the laminate for a printed circuit board has good machinability. It achieves halogen-free flame retardant, and has excellent heat and humidity resistance and heat resistance, low thermal expansion coefficient, low dielectric constant and dielectric loss, to meet the requirements of high-performance printed circuit board substrates and IC packaging.
- the present invention has been achieved by the following technical solutions.
- thermosetting resin composition comprising a composition and a solvent; the composition comprising the following components in parts by weight:
- Halogen-free epoxy resin 20 ⁇ 100 parts
- Nitrile-based resin 10 to 30 parts
- Allyl modified bismale resin prepolymer 20 ⁇ 100 parts
- Curing agent 20 ⁇ 100 parts
- the composition is dissolved in a solvent, and the weight percentage thereof is between 65% and 75% by weight.
- the nitrile-based resin has a low softening point, a low viscosity, and good fluidity, and has excellent flame retardancy, high temperature resistance, and dielectric properties.
- the present invention employs a nitrile-based resin to improve the flame retardancy of the thermosetting resin composition.
- the nitrile-based resin has insufficient toughness and poor mechanical processing, and the nitrile-based resin exhibits a strong hydrophilic property, and has poor compatibility with other components and is difficult to process.
- Bismaleimide has a fat segment of moderate length, and in the thermosetting resin composition of the present invention, a bismaleimide resin is used in combination with a nitrile-based resin and an epoxy resin to cure the resin composition.
- the nitrile group of the nitrile resin is subjected to preliminary polymerization to form a triazine ring, and copolymerizes with the epoxy group in the epoxy resin to form an oxazolidinone structure, which has good heat resistance and toughness, and Further improving the thermal stability of the resin composition; and the bismaleimide and the other resin of the system undergo a curing cross-linking reaction, and the double-maleimide five-membered heterocyclic ring and the aliphatic segment are combined to achieve Maintaining the high glass transition temperature, high heat resistance, and high heat and humidity resistance of the thermosetting resin, the toughness is improved and the processing difficulty is lowered.
- the viscosity of the bismaleimide resin is large, which makes the process control of the resin production process difficult, and the controllable production cannot be achieved.
- the present invention selects various raw materials in a thermosetting resin composition, and each The optimized configuration of the content between raw materials achieves the purpose of reducing the viscosity of the resin, solves the technical problem of difficult process control in the production process, and provides possibilities for controllable production.
- the present invention obtains UL-V0 excellent in toughness, machinability and water absorption by selecting an epoxy resin, a nitrile-based resin and an allyl-modified bismale resin prepolymer, and performing reasonable blending.
- Grade thermosetting resin composition obtained by selecting an epoxy resin, a nitrile-based resin and an allyl-modified bismale resin prepolymer, and performing reasonable blending.
- the epoxy resin is added in an amount of 20 to 100 parts, for example, 22 parts by weight, 26 parts by weight, 37 parts by weight, 42 parts by weight, 56 parts by weight, and 68 parts by weight. Parts, 75 parts by weight, 86 parts by weight, 98 parts by weight, and the like. If the amount of the halogen-free epoxy resin is too large, the brittleness of the material will increase, and if the amount is too small, the I peel strength will be lowered.
- Ar 1 is selected from any one of the following structures:
- the halogen-free epoxy resin has an epoxy equivalent of 200 to 2000, such as 250, 280, 306- 385, 420, 495, 552, 568, 590, 630, 687, 785, 842, 888, 963, 1085, 1257, 1586, 1768, 1890, 1950, and the like. If the epoxy equivalent of the halogen epoxy resin is too large, the viscosity of the composition will increase, and if it is too small, the crosslinking density will be too large.
- the nitrile-based resin is added in an amount of 10 to 30 parts, for example, 12 parts by weight, 16 parts by weight, 18 parts by weight, 22 parts by weight, 26 parts by weight, 28 parts by weight or the like. Excessive addition nitrile resin composition increases water absorption, is too small, will reduce the heat resistance of the material (preferably, the present invention is the nitrile group-containing resin is a polymer of a plurality of nitrile groups,
- Ar 2 is selected from any one of the following structures:
- the nitrile-based resin of the present invention can be prepared by a method of referring to a nitrile-based resin monomer (ie, a tetraphthalonitrile resin monomer containing a benzoxazine ring) described in CN102976972, or commercially available.
- a nitrile-based resin monomer ie, a tetraphthalonitrile resin monomer containing a benzoxazine ring
- the thermosetting resin composition of the present invention the allyl-modified bismale resin prepolymer is added in an amount of 20 to 100 parts, for example, 26 parts by weight, 38 parts by weight, 42 parts by weight, 55 parts by weight, 67 parts by weight, 79 parts by weight, 83 parts by weight, 96 parts by weight, and the like.
- the amount of the bismaleimide resin added is too large, the toughness of the material is adversely affected, and if it is too small, the heat resistance of the laminate is lowered.
- the allyl-modified bismale resin prepolymer is obtained by modifying a bismaleimide resin with a diallyl compound;
- the modification reaction temperature is 110 to 160 ° C, for example 118 ° C, 123 ° C, 135 ° C, 146 ° C, 154 ° C, 158 ° C, etc.
- modified reaction time is 20 ⁇ 120min, such as 30min, 40min, 60min, 75min, 88min, 96min, 105min, 117 min; wherein the mass ratio of the bismaleimide resin to the diallyl compound is preferably 100: (15 to 120), for example, 100: 18, 100: 24, 100: 38, 100: 45, 100: 64, 100:78, 100:86, 100:97, 100:108, 100:116, etc.
- the bismaleimide resin is selected from the group consisting of 4,4'-diphenylmethane bismaleimide resin, 4,4'-diphenyl ether bismaleimide resin, 4, 4' Any one or a combination of at least two of a diphenylisopropyl bismaleimide resin and a 4,4'-diphenylsulfone bismaleimide resin.
- the combination of the bismaleimide resin typically, but not limited to, 4,4'-diphenylmethane bismaleimide resin and 4,4'-diphenyl ether bismaleimide resin Combination, combination of 4,4'-diphenylisopropyl bismaleimide resin and 4,4'-diphenylmethane bismaleimide resin, 4,4'-diphenylisopropyl bismale Combination of imide resin, 4,4'-diphenyl sulfone bismaleimide resin and 4,4'-diphenylmethane bismaleimide resin, 4,4'-diphenyl ether double horse A combination of an imide resin, a 4,4'-diphenylisopropyl bismaleimide resin, and a 4,4'-diphenylsulfone bismaleimide resin.
- the diallyl compound is selected from the group consisting of diallyl bisphenol A, diallyl bisphenol S, allyl phenol oxyresin, allyl phenolic resin, diallyl diphenyl ether Any one or a combination of at least two.
- the combination of diallyl compounds is typically, but not limited to, selected from diallyl bisphenol A and dienes a combination of propyl bisphenol S, a combination of allyl phenoxy resin and diallyl diphenyl ether, a combination of allyl phenolic resin, diallyl diphenyl ether and diallyl bisphenol A, A combination of allyl bisphenol S, allyl phenoxy resin and diallyl diphenyl ether.
- the invention adopts an allyl compound and a bismaleimide resin to carry out chain extension reaction at a certain ratio to prepare an allyl modified bismale resin prepolymer, by increasing the length of the molecular chain in the resin and destroying the molecular chain regularity. To achieve the purpose of improving toughness and solubility.
- the curing agent of the present invention is capable of chemically reacting with a resin in a thermosetting resin composition to form a network-like solid polymer, which causes the linear resin to become a tough bulk solid.
- the curing agent is added in an amount of 20 to 100 parts, for example, 26 parts by weight, 32 parts by weight, 40 parts by weight, 45 parts by weight, 54 parts by weight, 62 parts by weight, or the like. 75 parts by weight, 87 parts by weight, 95 parts by weight, and the like.
- the curing agent of the present invention is selected from any one or a combination of at least two of dicyandiamide, aromatic amine, acid anhydride, phenolic curing agent, isocyanurate or novolac.
- the combination typically includes, but is not limited to, a combination of dicyandiamide and an aromatic amine, a combination of a phenolic curing agent and an acid anhydride, a combination of a trialluryl uric acid and a linear phenolic aldehyde, an aromatic amine, an acid anhydride, and a phenolic curing agent. Combination, etc.
- the filler is added in an amount of 10 to 100 parts, for example, 12 parts by weight, 15 parts by weight, 18 parts by weight, 22 parts by weight, 27 parts by weight, 35 parts by weight, 39 parts by weight. Parts, 47 parts by weight, 56 parts by weight, 75 parts by weight, 84 parts by weight, 88 parts by weight, 94 parts by weight, 98 parts by weight, and the like.
- the filler of the present invention is selected from any one or a combination of at least two of aluminum hydroxide, silica, magnesium hydroxide, kaolin, and hydrotalcite.
- the combination typically, but not exclusively, includes a combination of aluminum hydroxide and magnesium hydroxide, a combination of silica and kaolin, silica, magnesium hydroxide and hydrogen.
- thermosetting resin composition of the present invention is composed of a composition and a solvent, and the composition accounts for 65 to 75 wt%, such as 66%, 69%, 70%, 73%, 74%, etc., based on the total weight of the composition.
- the solvent of the present invention is selected from any one or a combination of at least two of a ketone solvent, a hydrocarbon solvent, an alcohol solvent, an ether solvent, an ester solvent or an aprotic solvent;
- the ketone solvent Preferably, it is preferably one or a combination of at least two of acetone, methyl ethyl ketone or methyl isobutyl ketone;
- the hydrocarbon solvent is preferably toluene and/or xylene;
- the alcohol solvent is preferably methanol, Any one or a combination of at least two of ethanol or n-propanol;
- the ether solvent is preferably ethylene glycol monomethyl ether and/or propylene glycol monomethyl ether; and
- the ester solvent is preferably propylene glycol methyl ether acetate and / or ethyl acetate;
- the aprotic solvent is preferably hydrazine, hydrazine-dimethylformamide
- the combination of solvents typically, but not limited to, includes a combination of acetone and methyl isobutyl ketone, a combination of ethanol and methanol, a combination of ethylene glycol monomethyl ether and methanol, ethyl acetate and hydrazine, hydrazine-dimethyl
- the composition of the present invention further comprises 0.01 to 1.0 part by weight of a curing accelerator.
- the content of the curing accelerator in the composition may be 0.02 parts by weight, 0.06 parts by weight, 0.2 parts by weight, 0.5 parts by weight, 0.7 parts by weight, 0.9 parts by weight, 0.92 parts by weight, 0.97 parts by weight or the like.
- the curing accelerator of the present invention is selected from any one or a combination of at least two of a tertiary amine, a tertiary phosphorus, a quaternary ammonium salt, a quaternary phosphonium salt or an imidazole compound.
- the combination typically, but not exclusively, includes a combination of a tertiary phosphorus and a tertiary amine, a combination of a quaternary ammonium salt and a quaternary phosphonium salt, a combination of an imidazole compound and a tertiary amine, a quaternary ammonium salt, a quaternary phosphonium salt, and an imidazole compound. Combination, etc.
- the resin composition of the present invention is composed of a composition and a solvent; the composition includes the following components in parts by weight: Halogen-free epoxy resin: 20 ⁇ 100 parts;
- Nitrile-based resin 10 to 30 parts
- Allyl modified bismale resin prepolymer 20 ⁇ 100 parts
- Curing agent 20 ⁇ 100 parts
- Curing accelerator 0.01 ⁇ 1.0 parts
- the composition is dissolved in a solvent, and the weight percentage of the composition in the total weight is between 65% and 75%.
- a known additive such as a coloring pigment, an antifoaming agent, a surfactant, a flame retardant, an ultraviolet absorber, an antioxidant, a flow regulator, etc., as needed, the type and amount of the additive.
- those skilled in the art can make a selection based on the expertise acquired.
- thermosetting resin composition of the present invention can be selected by those skilled in the art with reference to the preparation method of the existing resin composition, and the actual situation is selected, and the present invention is not particularly limited.
- a typical but non-limiting method of preparing a thermosetting resin composition includes the following steps:
- the formulation amount of the epoxy resin, the nitrile resin, the allyl modified buma resin prepolymer, the curing agent, the filler, the curing accelerator are added to the reaction vessel or the reaction kettle, and the solvent of the formula amount is added, and the mixture is uniformly stirred to obtain a solid.
- the allyl modified bismale resin prepolymer is prepared by: mixing a bismaleimide resin and a diallyl compound by a mass of 100: (15 ⁇ 120), and at 110 ⁇ The reaction was carried out at 160 ° C for 30 to 120 min to obtain an allyl modified bismale resin prepolymer.
- the prepreg according to the second aspect of the present invention comprises a reinforcing material and a base material impregnated on the reinforcing material, wherein the base material is a thermosetting resin composition according to any one of the objectives.
- the prepreg also known as "PP sheet” or “bonding sheet” is a sheet material prepared by impregnating a resin glue with a reinforcing material and pre-baking it by heat treatment.
- the prepreg will soften under heat and pressure, and will be reversed after cooling. Should be cured.
- the binder of the present invention is an inorganic or organic material.
- the inorganic material is selected from the group consisting of glass fibers, carbon fibers, boron fibers, metal woven fabrics, or nonwoven fabrics.
- the glass fiber cloth or nonwoven fabric is selected from any one of E-glass, Q-type cloth, NE cloth, D-type cloth, S-type cloth, and high-silicone cloth; and the glass fiber cloth is preferably E-glass.
- the organic material is selected from the group consisting of polyester, polyamine, polyacrylic acid, polyimide, aramid, polytetrafluoroethylene, or syndiotactic polystyrene woven or nonwoven or nonwoven paper.
- the typical but non-limiting preparation method of the prepreg includes the following steps:
- thermosetting resin composition glue a flat-surfaced base material (such as E-glass cloth), uniformly coating the glue of the thermosetting resin composition, and then baking, so that the thermosetting resin composition therein is in a semi-curing stage (B-stage), that is, The temperature of the baking is selected according to the boiling point of the solvent used for the thermosetting resin composition glue, generally 20 to 80 ° C, preferably 80 to 250 ° C, which is greater than the boiling point of the solvent, and the baking time. For l ⁇ 30min.
- the prepreg provided by the invention has good machinability, can realize halogen-free flame retardancy, and has excellent heat and humidity resistance, heat resistance, low thermal expansion coefficient, low dielectric constant and dielectric loss.
- a metal foil-clad laminate for a printed circuit according to the third aspect of the present invention comprising a laminate and a metal foil laminated on one side or both sides of the laminate, the laminate comprising a plurality of sheets for the purpose of bonding
- the prepreg is composed of a reinforcing material and a base material impregnated on the reinforcing material, and the base material is a thermosetting resin composition according to any one of the objectives.
- a laminate is a type of laminate which is a composite of two or more layers of resin-impregnated fibers or fabrics (i.e., prepregs) which are laminated and heat-pressed.
- the metal foil-clad laminate for printed circuit boards is obtained on a single-sided or double-sided metal foil of a conventional laminate.
- the metal foil of the present invention is a copper foil
- the method for preparing a laminate for a printed circuit comprises the following steps:
- hot press forming is carried out in a laminating apparatus, and hot press forming is preferably carried out by a stepwise pressing method (i.e., stepwise heating and pressure increasing).
- a stepwise pressing method i.e., stepwise heating and pressure increasing.
- the specific operating conditions of the stepwise pressing method are preferably:
- the temperature gradient was raised from room temperature to 150 ° C in 1 15 min for 30 min; 2 was raised to 180 ° C for 5 h in 5 min; 3 30 min was cooled to room temperature;
- the pressure gradient is from 0 to 0.6 MPa in 1 lmin, and the pressure is maintained for 30 min; in 2 lmin, it rises to l.OMPa, and the pressure is 2.5 h ;
- the post-treatment conditions are maintained at 200 ⁇ 245 °C for 1 to 5 hours.
- the copper-clad laminate provided by the present invention has good machinability, can achieve halogen-free flame retardancy, and has excellent heat and heat resistance, low thermal expansion coefficient, low dielectric constant and dielectric loss. Compared with the prior art, the present invention has the following beneficial effects:
- thermosetting resin composition of the present invention contains an allyl-modified bismale resin prepolymer, a nitrile-based resin, and a non-epoxy resin as a main component, and a bismaleimide resin is used as a main component.
- Change Improves the toughness and solubility of the thermosetting resin.
- nitrile-based resin By adding nitrile-based resin, the flame retardancy, heat resistance and low dielectric property of the thermosetting resin composition are improved, and a printed circuit of UL-V0 level is obtained.
- a halogen-free epoxy resin further improves the toughness and machinability of the thermosetting resin composition;
- the prepreg and the printed circuit board provided by the present invention have good machinability, can realize halogen-free flame retardancy, and have excellent heat and heat resistance, low thermal expansion coefficient, and low dielectric constant. Characteristics such as dielectric loss.
- Examples 1 to 11 provided 11 kinds of thermosetting resin compositions
- Comparative Examples 1 to 7 provided 7 kinds of resin compositions for comparison with the resin compositions provided in Examples 1 to 11; the examples 1 to 6
- the formulations of the resin compositions provided are shown in Table 1.
- the formulations of the resin compositions provided in Examples 7 to 11 are shown in Table 2; and the formulations of the resin compositions provided in Comparative Examples 1 to 7 are shown in Table 3.
- Diaminodiphenyl sulfone 8 1-1 one nitrogen phenol aldehyde one 10 20 20 aluminum hydroxide 10 10 5 10 40 silica 10 10 5 10 30 magnesium hydroxide 10 10 0 10 30 methoxy silane coupling agent 0.5 0.5 0.5 0.5 0.5
- DCPD is dicyclopentadiene epoxy resin, Japan DIC HP-7200H, epoxy equivalent 890g / mol
- biphenyl type is biphenyl type epoxy resin, SHIN-A SE-5000, epoxy equivalent 256g / mol
- Bisphenol F is bisphenol F epoxy resin, Shanghai Shi Yue KF21, epoxy equivalent 542g / mol
- the nitrile-based resin is prepared by the method of the nitrile-based resin monomer (ie, the tetraphthalamide resin monomer containing a benzoxazine ring) described in CN102976972, and the specific structure is as follows:
- Double horse 1 is the allyl modified bismale resin prepolymer obtained in Synthesis Example 1;
- Double horse 2 is the allyl modified bismale resin prepolymer obtained in Synthesis Example 2;
- Double horse 3 is the allyl modified bismale resin prepolymer obtained in Synthesis Example 3;
- Dicyandiamide purchased from Ningxia Darong;
- Linear novolac is 2812 purchased from Korea MOMENTIVE, hydroxyl equivalent 105g / mol ;
- Diaminodiphenyl sulfone purchased from Taiwan Liuhe Chemical Co., Ltd.;
- the nitrogen-containing phenolic aldehyde is A-125 purchased from Jinyi Chemical Co., with a hydroxyl equivalent of 125 g/mol ;
- Aluminum hydroxide the average material diameter is 1 ⁇ 5 ⁇ , and the purity is more than 99%;
- Silica the average material diameter is 1 ⁇ 3 ⁇ , and the purity is 99% or more;
- Magnesium hydroxide the average material diameter is 1 ⁇ 3 ⁇ , and the purity is more than 99%;
- thermosetting resin composition was uniformly obtained.
- the resin compositions provided in Examples 1 to 11 and Comparative Examples 1 to 7 were prepared as follows, and a metal foil-clad laminate was prepared as follows, and the prepared metal foil-clad laminate was subjected to performance test.
- thermosetting sheet The preparation method of the thermosetting sheet includes:
- thermosetting resin composition composite material The glue of the thermosetting resin composition was impregnated with a glass fiber cloth, and laminated to obtain a laminated glass cloth containing a dipping liquid, followed by heating and pressurizing at 250 ° C for 3 hours to obtain a thermosetting resin composition composite material.
- the performance test items and specific methods are:
- the peel strength of the metal cap layer was tested in accordance with the experimental conditions of "thermal stress" in the method specified in 2.4.8 of IPC-TM-650.
- TMA Thermal expansion coefficient Z-axis CTE
- the measurement was carried out in accordance with the method specified in 2.4.24 of IPC-TM-650.
- the measurement was carried out in accordance with the method specified in 2.4.26 of IPC-TM-650.
- the measurement was carried out in accordance with the method of 2.3.41 of IPC-TM-650.
- thermosetting sheets prepared from the resin compositions provided in Examples 1 to 6 are shown in Table 4; the results of the performance test of the thermosetting sheets prepared from the resin compositions provided in Examples 7 to 11 are shown in Table 5.
- the performance test results of the thermosetting sheets prepared from the resin compositions provided in Comparative Examples 1 to 7 are shown in Table 6.
- thermosetting sheet prepared by the resin compositions provided in Examples 1 to 6 Glass transition temperature Tg ( °c ) 175 180 185 200 190 183 Peel strength (N/mm) 1.66 1.72 1.70 1.83 1.89 1.76 Flammability (UL94) V-0 V-0 V-0 V-0 V-0 V- 0 Thermal stratification time (min) >60 >60 >60 >60 >60 >60 >60 Thermal expansion coefficient Z-axis CTE 2.9 2.6 2.7 2.5 2.4 2.4 (TMA) (30-260°C) %
- thermosetting resin composition of the present invention mainly comprises an allyl-modified bismale resin prepolymer, a nitrile-based resin and an epoxy-free epoxy resin, and a propylene-based compound to the double-malay
- the modification of the imide resin improves the toughness and solubility of the thermosetting resin
- the addition of the nitrile-based resin improves the flame retardancy, heat resistance and low dielectric property of the thermosetting resin composition, thereby obtaining UL- A laminate for printed circuit of V0 level
- the addition of a halogen-free epoxy resin further improves the toughness and machinability of the thermosetting resin composition.
- the resin composition of the present invention contains no halogen and phosphorus, and has a flame retardancy of UL94-V0 grade; a prepreg and a copper-clad laminate obtained therefrom have high heat resistance, high reliability, and high glass transition temperature. (Tg), flame retardancy, low water absorption, low dielectric loss and low expansion coefficient, and good processing properties.
- Tg glass transition temperature
Abstract
A thermoset resin composition consists of a composition and a solvent. The composition comprises, based on weight parts, the following components: halogen-free epoxy resin: 20-100 parts; nitrile resin: 10-30 parts; allyl modified bismaleimide resin prepolymer: 20-100 parts; a curing agent: 20-100 parts; and a filler: 10-100 parts. The composition is soluble in the solvent and the percentage of the weight of the composition to a total weight is 65-75wt%. The thermoset composition is provided with excellent tenacity, machinability and water absorbency. The flame retardancy reaches UL94-V0.
Description
一种热固性树脂组合物 技术领域 Thermosetting resin composition
本发明涉及一种树脂组合物， 具体涉及一种热固性树脂组合物及用其制成 的半固化片和印制电路用层压板， 属于电子材料技术领域， 可应用于集成电路 封装、 高频高速及高密度互连。 The present invention relates to a resin composition, in particular to a thermosetting resin composition and a prepreg and a laminate for the same, which are applicable to the field of electronic materials, and can be applied to integrated circuit packages, high-frequency high-speed and high Density interconnection.
背景技术 Background technique
当前， 在多功能化、 高性能化及轻量薄型化的带动下， 电子产业发展迅速。 以 IC封装为例， 由起初的通孔插装 （PTH Insertion) 方式， 逐渐过渡到表面贴 装（SMT)方式， 然后又演变到到现在以 BGA、 CSP及 Flip Chip为主要封装形 式。 快速发展的技术对印制线路板及覆铜板提出了更为严苛的要求。 如要求相 关产品具有环保阻燃性， 高耐热性， 高耐湿热性， 低热膨胀系数， 及高弹性模 量等一系列优异的综合性能。 At present, the electronics industry is developing rapidly due to its multi-functionality, high performance and light weight. Taking the IC package as an example, the initial PTH Insertion method gradually transitioned to the surface mount (SMT) mode, and then evolved to the current BGA, CSP and Flip Chip as the main package form. Rapidly evolving technologies place even more stringent requirements on printed circuit boards and copper clad laminates. For example, the related products are required to have a series of excellent comprehensive properties such as environmentally friendly flame retardancy, high heat resistance, high heat and humidity resistance, low thermal expansion coefficient, and high elastic modulus.
本领域应用较为广泛的基材树脂包括聚苯醚、 双马来酰亚胺-三嗪树脂（BT 树脂）、 聚酰亚胺以及高耐热性环氧树脂等。 Substrate resins widely used in the art include polyphenylene ether, bismaleimide-triazine resin (BT resin), polyimide, and high heat resistant epoxy resin.
其中， 双马来酰亚胺（BMI)是以马来酰亚胺为活性端基的一类双官能团化 合物， 具有优异的电绝缘性、 透波性、 阻燃性、 耐热性、 耐辐射， 以及良好的 力学性能和尺寸稳定性， 并且具有与环氧树脂相近的流动性和可塑性， 因此， 其成型工艺与环氧树脂相近。 双马来酰亚胺现已成为高性能复合材料合成与制 备中非常重要以及最为常用的一类树脂基体， 如可制成耐高温绝缘材料或胶粘 剂等广泛地应用于汽车制造、 电子产品、 机械、 航天航空等领域。 Among them, bismaleimide (BMI) is a kind of bifunctional compound with maleimide as active end group, which has excellent electrical insulation, wave permeability, flame retardancy, heat resistance and radiation resistance. , as well as good mechanical properties and dimensional stability, and have similar fluidity and plasticity to epoxy resin, so the molding process is similar to epoxy resin. Bismaleimide has become a very important and most commonly used resin matrix in the synthesis and preparation of high performance composite materials. For example, it can be made into high temperature insulating materials or adhesives, which are widely used in automobile manufacturing, electronic products, machinery. , aerospace and other fields.
但双马来酰亚胺也存在诸多不足， 比如： 其熔点为 150°C， 只能溶解于强极 性的溶剂中； 其固化产物脆性大， 抗冲击强度低、 固化温度高等； 此外， 双马
来酰亚胺结构中虽存在苯环以及氮元素， 使其具有一定的阻燃性能， 但是无法 满足实际应用中 UL-V0的要求。 所述双马来酰亚胺的缺点限制了其应用范围， 需要对其进行相应改性， 以满足不同的需求。 However, bismaleimide also has many disadvantages, such as: its melting point is 150 ° C, it can only be dissolved in a solvent with strong polarity; its cured product has high brittleness, low impact strength, high curing temperature, etc. Horse Although the benzene ring and the nitrogen element are present in the imide structure, it has a certain flame retardant property, but it cannot meet the requirements of UL-V0 in practical applications. The disadvantages of the bismaleimide limit its scope of application and require corresponding modification to meet different needs.
CN102344567A公开了一种改性双马来酰亚胺树脂的制备方法，具体的步骤 是加热混合酰胺酰亚胺树脂与双马来酰亚胺形成一种新型的改性双马来酰亚胺 树脂； 并将所述新型改性双马来酰亚胺树脂与氧化铝、 氮化铝、 碳化硅、 氮化 硼或其混合物等导热粉体混合制备成树脂组合物， 应用于软式电路板、 硬式电 路板、 集成电路封装、 液晶显示器封装或发光二极管封装等领域。 该方法提高 了双马来胺酰亚胺树脂的耐热性， 达到了热固性的目的， 但仍然没有有效的改 善双马来胺酰亚胺树脂的脆性问题， 并且材料交联密度大， 容易对材料的剥离 强度造成不利影响。 CN102344567A discloses a preparation method of modified bismaleimide resin, the specific step is to heat mixing amide imide resin and bismaleimide to form a novel modified bismaleimide resin. And mixing the novel modified bismaleimide resin with a thermally conductive powder such as alumina, aluminum nitride, silicon carbide, boron nitride or a mixture thereof to prepare a resin composition, which is applied to a flexible circuit board, Hard circuit boards, integrated circuit packages, liquid crystal display packages or LED packages. The method improves the heat resistance of the bismaleimide resin and achieves the purpose of thermosetting, but still does not effectively improve the brittleness of the bismaleimide resin, and the material has a high crosslink density, which is easy to The peel strength of the material adversely affects.
CN1398274 公开了一种用于制造印刷电路板绝缘夹层的无卤树脂混合料， 包含环氧基树脂和具有热固性的马来酰亚胺化合物， 所述的环氧基树脂中含有 氮含量为 5〜25wt%的环氧树脂固化剂。 所述无 ^树脂混合料是将所述组合物溶 于有机溶剂形成的。 所述混合料制备而成的覆铜板可达到无卤阻燃、 高耐热、 优良防水和高剥离强度等优异的综合性能； 但所述方案仍然没有解决马来酰亚 胺的脆性问题， 再加上环氧树脂本身也是一种脆性材料， 因此由该组合物得到 的复合材料的冲击强度等机械性能以及钻工加工性能难以满足实际的生产和应 用要求。 CN1398274 discloses a halogen-free resin mixture for manufacturing a printed circuit board insulating interlayer, comprising an epoxy resin and a thermosetting maleimide compound, wherein the epoxy resin contains a nitrogen content of 5~ 25wt% epoxy resin curing agent. The resin-free mixture is formed by dissolving the composition in an organic solvent. The copper clad laminate prepared by the mixture can achieve excellent comprehensive properties such as halogen-free flame retardant, high heat resistance, excellent water resistance and high peel strength; however, the solution still does not solve the brittleness problem of maleimide, and then In addition, the epoxy resin itself is also a brittle material, so that the mechanical properties such as impact strength and the drillability of the composite material obtained from the composition are difficult to meet the actual production and application requirements.
CN101652026 公开了一种制备覆铜板的方法： 先按照一定的重量比将双马 来酰亚胺树脂和烯丙基化合物混合并加热制得预聚体， 并将该预聚体配成溶液; 然后将含磷环氧树脂、 复合固化剂和固化促进剂加入预聚体溶液， 搅拌均匀得 到胶液并制成半固化片压制得到覆铜板。 该方法利用烯丙基化合物改性双马来
酰亚胺树脂， 增加了分子链的长度和破坏了分子链的规整性， 达到了提高材料 韧性及溶解性的目的； 且所得覆铜板可达到无卤阻燃的要求， 且耐热性、 耐湿 热性良好， 低介电损耗， 加工韧性优异。 但该方案中使用了含磷环氧树脂， 其 与烯丙基改性的双马来酰亚胺树脂比例不当会出现相容性问题， 并可能对复合 材料的耐热性能 （如 Tg， 耐湿热性能） 造成不利影响， 增加了该方案的实施难 因此， 本领域亟待开发一种热固性树脂组合物， 所述组合物需要提供一种 改性的双马来酰亚胺树脂， 且在保证优异的电绝缘性、 透波性、 阻燃性、 耐热 性、 耐辐射性， 以及良好的力学性能和尺寸稳定性， 流动性和可塑性的同时， 提供良好的韧性、 机械加工性和溶剂溶解性， 且具有 UL-V0的阻燃性。 CN101652026 discloses a method for preparing a copper clad plate: firstly mixing and heating a bismaleimide resin and an allyl compound according to a certain weight ratio to prepare a prepolymer, and formulating the prepolymer into a solution; The phosphorus-containing epoxy resin, the composite curing agent and the curing accelerator are added to the prepolymer solution, and the mixture is uniformly stirred to obtain a glue solution, which is pressed into a prepreg to obtain a copper clad laminate. The method utilizes an allyl compound to modify the double horse The imide resin increases the length of the molecular chain and destroys the regularity of the molecular chain, thereby achieving the purpose of improving the toughness and solubility of the material; and the obtained copper clad plate can meet the requirement of halogen-free flame retardant, and has heat resistance and resistance. Good wet heat, low dielectric loss, and excellent processing toughness. However, phosphorus-containing epoxy resins are used in this scheme, and compatibility with ally-modified bismaleimide resin may cause compatibility problems, and may be resistant to heat resistance of composite materials (such as Tg, resistance). Damp heat performance) adversely affects the implementation of the solution. Therefore, there is a need in the art to develop a thermosetting resin composition which is required to provide a modified bismaleimide resin and is excellent in guarantee Electrical insulation, wave permeability, flame retardancy, heat resistance, radiation resistance, good mechanical properties and dimensional stability, fluidity and plasticity, providing good toughness, machinability and solvent solubility And has the flame retardancy of UL-V0.
发明内容 Summary of the invention
本发明的目的之一在于提供一种热固性树脂组合物， 所述组合物具有优异 的电绝缘性、 透波性、 阻燃性、 耐热性、 耐辐射， 以及良好的力学性能和尺寸 稳定性， 流动性和可塑性， 且通过调节组合物中各组分的种类和含量， 使所述 树脂组合物不仅具有良好的韧性、 机械加工性和溶剂溶解性， 能够实现无卤阻 燃具有 UL-V0的阻燃性。 One of the objects of the present invention is to provide a thermosetting resin composition which has excellent electrical insulating properties, wave permeability, flame retardancy, heat resistance, radiation resistance, and good mechanical properties and dimensional stability. , fluidity and plasticity, and by adjusting the kind and content of each component in the composition, the resin composition not only has good toughness, machinability and solvent solubility, but also can achieve halogen-free flame retardant with UL-V0 Flame retardant.
本发明的目的之二在于提供一种使用目的之一所述的热固性树脂组合物制 成的半固化片， 所述半固化片具备良好的机械加工性， 可实现无卤阻燃， 且具 有优良的耐湿热性和耐热性、 低热膨胀系数及低介电常数和介电损耗等特性。 Another object of the present invention is to provide a prepreg made of a thermosetting resin composition according to one of the objects of use, which has good machinability, can achieve halogen-free flame retardancy, and has excellent heat and humidity resistance. And heat resistance, low coefficient of thermal expansion, low dielectric constant and dielectric loss.
本发明的目的之三在于提供一种使用目的之一所述的热固性树脂组合物制 成的印制电路用覆金属箔层压板， 所述印制电路用层压板具备良好的机械加工 性， 可实现无卤阻燃， 且具有优良的耐湿热性和耐热性、 低热膨胀系数及低介 电常数和介电损耗等特性， 以满足高性能印制线路板基材及 IC封装要求。
本发明是通过如下技术方案实现的。 A third object of the present invention is to provide a metal foil-clad laminate for a printed circuit made of a thermosetting resin composition according to any one of the above aspects, wherein the laminate for a printed circuit board has good machinability. It achieves halogen-free flame retardant, and has excellent heat and humidity resistance and heat resistance, low thermal expansion coefficient, low dielectric constant and dielectric loss, to meet the requirements of high-performance printed circuit board substrates and IC packaging. The present invention has been achieved by the following technical solutions.
一种热固性树脂组合物， 由组成物和溶剂组成； 所述组成物按重量份数包 括如下组分： A thermosetting resin composition comprising a composition and a solvent; the composition comprising the following components in parts by weight:
无卤环氧树脂： 20〜100份； Halogen-free epoxy resin: 20~100 parts;
腈基树脂： 10〜30份； Nitrile-based resin: 10 to 30 parts;
烯丙基改性双马树脂预聚体： 20〜100份； Allyl modified bismale resin prepolymer: 20~100 parts;
固化剂： 20〜100份； Curing agent: 20~100 parts;
填料： 10〜100份； Filler: 10~100 parts;
其中， 组成物溶于溶剂， 并且其占总重的重量百分比为 65%〜75%之间。 腈基树脂具有较低的软化点、 较低的粘度和较好的流动性， 且具有优异的 阻燃性、 耐高温性和介电性能。 本发明选用腈基树脂来提高热固性树脂组合物 的阻燃性能。 但是单纯的腈基树脂的韧性不足， 机械加工方面表现欠佳， 且腈 基树脂表现出很强的亲水性质， 在与其他组分的配伍性不好， 加工难度大。 Wherein, the composition is dissolved in a solvent, and the weight percentage thereof is between 65% and 75% by weight. The nitrile-based resin has a low softening point, a low viscosity, and good fluidity, and has excellent flame retardancy, high temperature resistance, and dielectric properties. The present invention employs a nitrile-based resin to improve the flame retardancy of the thermosetting resin composition. However, the nitrile-based resin has insufficient toughness and poor mechanical processing, and the nitrile-based resin exhibits a strong hydrophilic property, and has poor compatibility with other components and is difficult to process.
双马来酰亚胺具有长度适中的脂肪链段， 在本发明所述的热固性树脂组合 物中， 利用双马来酰亚胺树脂与腈基树脂和环氧树脂配合， 在树脂组合物的固 化阶段， 腈基树脂的腈基经过初步聚合形成的三嗪环， 与环氧树脂中的环氧基 团发生共聚反应， 生成恶唑烷酮结构， 该结构具有良好的耐热性能和韧性， 且 进一步提高了树脂组合物的热稳定性； 且双马来酰亚胺与体系其他树脂发生固 化交联反应， 在双马来酰亚胺五元杂环和脂肪链段的共同作用下， 达到了保持 热固性树脂高玻璃化转变温度、 高耐热性、 高耐湿热性的同时， 提高韧性， 降 低加工难度的目的。 Bismaleimide has a fat segment of moderate length, and in the thermosetting resin composition of the present invention, a bismaleimide resin is used in combination with a nitrile-based resin and an epoxy resin to cure the resin composition. In the stage, the nitrile group of the nitrile resin is subjected to preliminary polymerization to form a triazine ring, and copolymerizes with the epoxy group in the epoxy resin to form an oxazolidinone structure, which has good heat resistance and toughness, and Further improving the thermal stability of the resin composition; and the bismaleimide and the other resin of the system undergo a curing cross-linking reaction, and the double-maleimide five-membered heterocyclic ring and the aliphatic segment are combined to achieve Maintaining the high glass transition temperature, high heat resistance, and high heat and humidity resistance of the thermosetting resin, the toughness is improved and the processing difficulty is lowered.
双马来酰亚胺树脂的黏度较大， 造成树脂的生产过程工艺控制困难， 无法 实现可控化生产。 本发明通过对热固性树脂组合物中各种原料的选择， 以及各
原料间含量的优化配置， 实现了降低树脂粘度的目的， 解决了生产过程工艺控 制困难的技术问题， 为可控化生产提供了可能性。 The viscosity of the bismaleimide resin is large, which makes the process control of the resin production process difficult, and the controllable production cannot be achieved. The present invention selects various raw materials in a thermosetting resin composition, and each The optimized configuration of the content between raw materials achieves the purpose of reducing the viscosity of the resin, solves the technical problem of difficult process control in the production process, and provides possibilities for controllable production.
由此， 本发明通过选用环氧树脂、 腈基树脂和烯丙基改性双马树脂预聚体， 并进行合理的配合， 得到了韧性、 机械加工性和吸水性均表现优异的 UL-V0级 的热固性树脂组合物。 Thus, the present invention obtains UL-V0 excellent in toughness, machinability and water absorption by selecting an epoxy resin, a nitrile-based resin and an allyl-modified bismale resin prepolymer, and performing reasonable blending. Grade thermosetting resin composition.
本发明所述的热固性树脂组合物， 组成物中无^环氧树脂的添加量为 20〜100份， 例如 22重量份、 26重量份、 37重量份、 42重量份、 56重量份、 68 重量份、 75重量份、 86重量份、 98重量份等。 无卤环氧树脂的添加量过多， 会 增大材料的脆性， 过少， 会导致 I剥离强度降低。
In the thermosetting resin composition of the present invention, the epoxy resin is added in an amount of 20 to 100 parts, for example, 22 parts by weight, 26 parts by weight, 37 parts by weight, 42 parts by weight, 56 parts by weight, and 68 parts by weight. Parts, 75 parts by weight, 86 parts by weight, 98 parts by weight, and the like. If the amount of the halogen-free epoxy resin is too large, the brittleness of the material will increase, and if the amount is too small, the I peel strength will be lowered.
其中， Ar1选自如下结构中的任意 1种: Wherein Ar 1 is selected from any one of the following structures:
优选地， 所述无卤环氧树脂的环氧当量为 200〜2000， 例如 250、 280、 306-
385、 420、 495、 552、 568、 590、 630、 687、 785、 842、 888、 963、 1085、 1257、 1586、 1768、 1890、 1950等。 卤环氧树脂的环氧当量过大， 会导致组合物粘房 增大 ， 过小， 会造成交联密度过大。 Preferably, the halogen-free epoxy resin has an epoxy equivalent of 200 to 2000, such as 250, 280, 306- 385, 420, 495, 552, 568, 590, 630, 687, 785, 842, 888, 963, 1085, 1257, 1586, 1768, 1890, 1950, and the like. If the epoxy equivalent of the halogen epoxy resin is too large, the viscosity of the composition will increase, and if it is too small, the crosslinking density will be too large.
组成物中腈基树脂的添加量为 10〜30份 例如 12重量份、 16重量份、 18重量份、 22重量份、 26重量份、 28重量份等。 腈基树脂的添加量过多， 会增大组合物吸水率， 过少， 会降低材料的耐热性能( 优选地， 本发明所述腈基树脂为含有多个腈基的高分子体， The nitrile-based resin is added in an amount of 10 to 30 parts, for example, 12 parts by weight, 16 parts by weight, 18 parts by weight, 22 parts by weight, 26 parts by weight, 28 parts by weight or the like. Excessive addition nitrile resin composition increases water absorption, is too small, will reduce the heat resistance of the material (preferably, the present invention is the nitrile group-containing resin is a polymer of a plurality of nitrile groups,
其中， Ar2选自如下结构中的任意 1种: Wherein Ar 2 is selected from any one of the following structures:
本发明所述腈基树脂可以参照 CN102976972所述腈基树脂单体 （即含苯并 恶嗪环的四邻苯二甲腈树脂单体） 的方法制备得到， 或者通过商购获得
本发明所述的热固性树脂组合物， 组成物中烯丙基改性双马树脂预聚体的 添加量为 20〜100份， 例如 26重量份、 38重量份、 42重量份、 55重量份、 67 重量份、 79重量份、 83重量份、 96重量份等。双马来酰亚胺树脂的添加量过多， 会对材料韧性产生不利影响， 过少， 会造成层压板的耐热性降低。 The nitrile-based resin of the present invention can be prepared by a method of referring to a nitrile-based resin monomer (ie, a tetraphthalonitrile resin monomer containing a benzoxazine ring) described in CN102976972, or commercially available. In the thermosetting resin composition of the present invention, the allyl-modified bismale resin prepolymer is added in an amount of 20 to 100 parts, for example, 26 parts by weight, 38 parts by weight, 42 parts by weight, 55 parts by weight, 67 parts by weight, 79 parts by weight, 83 parts by weight, 96 parts by weight, and the like. When the amount of the bismaleimide resin added is too large, the toughness of the material is adversely affected, and if it is too small, the heat resistance of the laminate is lowered.
优选地， 所述烯丙基改性双马树脂预聚体为双马来酰亚胺树脂经二烯丙基 化合物改性得到的； 所述改性的反应温度为 110〜160°C， 例如 118°C、 123 °C、 135°C、 146°C、 154°C、 158°C等， 改性的反应时间为 20〜120min， 例如 30min、 40min、 60min、 75min、 88min、 96min、 105min、 117min等； 其中， 双马来酰 亚胺树脂和二烯丙基化合物的质量比优选为 100: ( 15〜120 )， 例如 100: 18、 100:24、 100:38、 100:45、 100:64、 100:78、 100:86、 100:97、 100: 108、 100: 116 等。 Preferably, the allyl-modified bismale resin prepolymer is obtained by modifying a bismaleimide resin with a diallyl compound; the modification reaction temperature is 110 to 160 ° C, for example 118 ° C, 123 ° C, 135 ° C, 146 ° C, 154 ° C, 158 ° C, etc., modified reaction time is 20~120min, such as 30min, 40min, 60min, 75min, 88min, 96min, 105min, 117 min; wherein the mass ratio of the bismaleimide resin to the diallyl compound is preferably 100: (15 to 120), for example, 100: 18, 100: 24, 100: 38, 100: 45, 100: 64, 100:78, 100:86, 100:97, 100:108, 100:116, etc.
优选地，所述双马来酰亚胺树脂选自 4,4'-二苯甲烷双马来酰亚胺树脂、4,4'- 二苯醚双马来酰亚胺树脂、 4,4'-二苯异丙基双马来酰亚胺树脂、 4,4'-二苯砜双马 来酰亚胺树脂中的任意 1种或至少 2种的组合。 Preferably, the bismaleimide resin is selected from the group consisting of 4,4'-diphenylmethane bismaleimide resin, 4,4'-diphenyl ether bismaleimide resin, 4, 4' Any one or a combination of at least two of a diphenylisopropyl bismaleimide resin and a 4,4'-diphenylsulfone bismaleimide resin.
所述双马来酰亚胺树脂的组合典型但非限制性的包括 4,4'-二苯甲烷双马来 酰亚胺树脂和 4,4'-二苯醚双马来酰亚胺树脂的组合， 4,4'-二苯异丙基双马来酰 亚胺树脂和 4,4'-二苯甲烷双马来酰亚胺树脂的组合， 4,4'-二苯异丙基双马来酰 亚胺树脂、 4,4'-二苯砜双马来酰亚胺树脂和 4,4'-二苯甲烷双马来酰亚胺树脂的 组合， 4,4'-二苯醚双马来酰亚胺树脂、 4,4'-二苯异丙基双马来酰亚胺树脂和 4,4'- 二苯砜双马来酰亚胺树脂的组合等。 The combination of the bismaleimide resin typically, but not limited to, 4,4'-diphenylmethane bismaleimide resin and 4,4'-diphenyl ether bismaleimide resin Combination, combination of 4,4'-diphenylisopropyl bismaleimide resin and 4,4'-diphenylmethane bismaleimide resin, 4,4'-diphenylisopropyl bismale Combination of imide resin, 4,4'-diphenyl sulfone bismaleimide resin and 4,4'-diphenylmethane bismaleimide resin, 4,4'-diphenyl ether double horse A combination of an imide resin, a 4,4'-diphenylisopropyl bismaleimide resin, and a 4,4'-diphenylsulfone bismaleimide resin.
优选地， 所述二烯丙基化合物选自二烯丙基双酚 A、 二烯丙基双酚 S、烯丙 基酚氧树脂、 烯丙基酚醛树脂、 二烯丙基二苯醚中的任意 1种或至少 2种的组 合。 所述二烯丙基化合物的组合典型但非限制性的选自二烯丙基双酚 A和二烯
丙基双酚 S 的组合， 烯丙基酚氧树脂和二烯丙基二苯醚的组合， 烯丙基酚醛树 脂、 二烯丙基二苯醚和二烯丙基双酚 A的组合， 二烯丙基双酚 S、 烯丙基酚氧 树脂和二烯丙基二苯醚的组合等。 Preferably, the diallyl compound is selected from the group consisting of diallyl bisphenol A, diallyl bisphenol S, allyl phenol oxyresin, allyl phenolic resin, diallyl diphenyl ether Any one or a combination of at least two. The combination of diallyl compounds is typically, but not limited to, selected from diallyl bisphenol A and dienes a combination of propyl bisphenol S, a combination of allyl phenoxy resin and diallyl diphenyl ether, a combination of allyl phenolic resin, diallyl diphenyl ether and diallyl bisphenol A, A combination of allyl bisphenol S, allyl phenoxy resin and diallyl diphenyl ether.
本发明采用烯丙基化合物与双马来酰亚胺树脂以一定比例进行扩链反应制 备得到烯丙基改性双马树脂预聚体， 通过增加树脂中分子链的长度和破坏分子 链的规整性来达到提高韧性及溶解性的目的。 The invention adopts an allyl compound and a bismaleimide resin to carry out chain extension reaction at a certain ratio to prepare an allyl modified bismale resin prepolymer, by increasing the length of the molecular chain in the resin and destroying the molecular chain regularity. To achieve the purpose of improving toughness and solubility.
本发明所述固化剂能够与热固性树脂组合物中的树脂发生化学反应， 形成 网状立体聚合物， 使线型树脂变成坚韧的体型固体。 本发明所述的热固性树脂 组合物中， 组成物中固化剂的添加量为 20〜100份， 例如 26重量份、 32重量份、 40重量份、 45重量份、 54重量份、 62重量份、 75重量份、 87重量份、 95重量 份等。 固化剂的添加量过多， 超过 100重量份， 会引起树脂固化物耐热性变差， 过少， 低于 20重量份， 会引起树脂组合物固化不足， 玻璃化转变温度降低。 The curing agent of the present invention is capable of chemically reacting with a resin in a thermosetting resin composition to form a network-like solid polymer, which causes the linear resin to become a tough bulk solid. In the thermosetting resin composition of the present invention, the curing agent is added in an amount of 20 to 100 parts, for example, 26 parts by weight, 32 parts by weight, 40 parts by weight, 45 parts by weight, 54 parts by weight, 62 parts by weight, or the like. 75 parts by weight, 87 parts by weight, 95 parts by weight, and the like. When the amount of the curing agent added is too large, more than 100 parts by weight causes the heat resistance of the cured resin to deteriorate, and if it is too small, less than 20 parts by weight, the curing of the resin composition is insufficient, and the glass transition temperature is lowered.
优选地， 本发明所述固化剂选自双氰胺、 芳香胺、 酸酐、 酚类固化剂、 异 氰尿酸三烯酯或线性酚醛中的任意 1种或至少 2种的组合。 所述组合典型但非 限制性的包括双氰胺和芳香胺的组合， 酚类固化剂和酸酐的组合， 异氰尿酸三 烯酯和线性酚醛的组合， 芳香胺、 酸酐和酚类固化剂的组合等。 Preferably, the curing agent of the present invention is selected from any one or a combination of at least two of dicyandiamide, aromatic amine, acid anhydride, phenolic curing agent, isocyanurate or novolac. The combination typically includes, but is not limited to, a combination of dicyandiamide and an aromatic amine, a combination of a phenolic curing agent and an acid anhydride, a combination of a trialluryl uric acid and a linear phenolic aldehyde, an aromatic amine, an acid anhydride, and a phenolic curing agent. Combination, etc.
本发明所述的热固性树脂组合物， 组成物中填料的添加量为 10〜100份， 例 如 12重量份、 15重量份、 18重量份、 22重量份、 27重量份、 35重量份、 39 重量份、 47重量份、 56重量份、 75重量份、 84重量份、 88重量份、 94重量份、 98重量份等。 In the thermosetting resin composition of the present invention, the filler is added in an amount of 10 to 100 parts, for example, 12 parts by weight, 15 parts by weight, 18 parts by weight, 22 parts by weight, 27 parts by weight, 35 parts by weight, 39 parts by weight. Parts, 47 parts by weight, 56 parts by weight, 75 parts by weight, 84 parts by weight, 88 parts by weight, 94 parts by weight, 98 parts by weight, and the like.
优选地， 本发明所述填料选自氢氧化铝、 二氧化硅、 氢氧化镁、 高岭土、 水滑石中的任意 1种或至少 2种的组合。 所述组合典型但非限制性的包括氢氧 化铝和氢氧化镁的组合， 二氧化硅和高岭土的组合， 二氧化硅、 氢氧化镁和氢
氧化铝的组合， 高岭土、 水滑石和二氧化硅的组合等。 Preferably, the filler of the present invention is selected from any one or a combination of at least two of aluminum hydroxide, silica, magnesium hydroxide, kaolin, and hydrotalcite. The combination typically, but not exclusively, includes a combination of aluminum hydroxide and magnesium hydroxide, a combination of silica and kaolin, silica, magnesium hydroxide and hydrogen. A combination of alumina, a combination of kaolin, hydrotalcite and silica.
本发明所述的热固性树脂组合物由组成物和溶剂组成， 且组成物占组合物 总重量的 65〜75wt%， 例如 66%、 69%、 70%、 73%、 74%等。 The thermosetting resin composition of the present invention is composed of a composition and a solvent, and the composition accounts for 65 to 75 wt%, such as 66%, 69%, 70%, 73%, 74%, etc., based on the total weight of the composition.
优选地， 本发明所述溶剂选自酮类溶剂、 烃类溶剂、 醇类溶剂、 醚类溶剂、 酯类溶剂或非质子溶剂中的任意 1种或至少 2种的组合； 所述酮类溶剂优选自 丙酮、 甲基乙基酮或甲基异丁基酮中的任意 1种或至少 2种的组合； 所述烃类 溶剂优选甲苯和 /或二甲苯； 所述醇类溶剂优选自甲醇、 乙醇、 或正丙醇中的任 意 1种或至少 2种的组合；所述醚类溶剂优选乙二醇单甲醚和 /或丙二醇单甲醚; 所述酯类溶剂优选丙二醇甲醚醋酸酯和 /或乙酸乙酯； 所述非质子溶剂优选 Ν,Ν- 二甲基甲酰胺和 /或 Ν,Ν-二乙基甲酰胺。 Preferably, the solvent of the present invention is selected from any one or a combination of at least two of a ketone solvent, a hydrocarbon solvent, an alcohol solvent, an ether solvent, an ester solvent or an aprotic solvent; the ketone solvent Preferably, it is preferably one or a combination of at least two of acetone, methyl ethyl ketone or methyl isobutyl ketone; the hydrocarbon solvent is preferably toluene and/or xylene; and the alcohol solvent is preferably methanol, Any one or a combination of at least two of ethanol or n-propanol; the ether solvent is preferably ethylene glycol monomethyl ether and/or propylene glycol monomethyl ether; and the ester solvent is preferably propylene glycol methyl ether acetate and / or ethyl acetate; the aprotic solvent is preferably hydrazine, hydrazine-dimethylformamide and/or hydrazine, hydrazine-diethylformamide.
所述溶剂的组合典型但非限制性的包括丙酮和甲基异丁基酮的组合， 乙醇 和甲醇的组合， 乙二醇单甲醚和甲醇的组合， 乙酸乙酯和 Ν,Ν-二甲基甲酰胺的 组合， 丙二醇甲醚醋酸酯、 乙酸乙酯和的甲基乙基酮组合， 甲醇、 乙醇和丙二 醇甲醚醋酸酯的组合等。 The combination of solvents typically, but not limited to, includes a combination of acetone and methyl isobutyl ketone, a combination of ethanol and methanol, a combination of ethylene glycol monomethyl ether and methanol, ethyl acetate and hydrazine, hydrazine-dimethyl A combination of carbamide, propylene glycol methyl ether acetate, a combination of ethyl acetate and methyl ethyl ketone, a combination of methanol, ethanol and propylene glycol methyl ether acetate, and the like.
作为优选， 本发明所述组成物还包括 0.01〜1.0重量份的固化促进剂。 所述 组成物中固化促进剂的含量可以是 0.02重量份、 0.06重量份、 0.2重量份、 0.5 重量份、 0.7重量份、 0.9重量份、 0.92重量份、 0.97重量份等。 Preferably, the composition of the present invention further comprises 0.01 to 1.0 part by weight of a curing accelerator. The content of the curing accelerator in the composition may be 0.02 parts by weight, 0.06 parts by weight, 0.2 parts by weight, 0.5 parts by weight, 0.7 parts by weight, 0.9 parts by weight, 0.92 parts by weight, 0.97 parts by weight or the like.
优选地， 本发明所述固化促进剂选自三级胺、 三级磷、 季胺盐、 季磷盐或 咪唑化合物中的任意 1种或至少 2种的组合。 所述组合典型但非限制性的包括 三级磷和三级胺的组合， 季胺盐和季磷盐的组合， 咪唑化合物和三级胺的组合， 季胺盐、 季磷盐和咪唑化合物的组合等。 Preferably, the curing accelerator of the present invention is selected from any one or a combination of at least two of a tertiary amine, a tertiary phosphorus, a quaternary ammonium salt, a quaternary phosphonium salt or an imidazole compound. The combination typically, but not exclusively, includes a combination of a tertiary phosphorus and a tertiary amine, a combination of a quaternary ammonium salt and a quaternary phosphonium salt, a combination of an imidazole compound and a tertiary amine, a quaternary ammonium salt, a quaternary phosphonium salt, and an imidazole compound. Combination, etc.
作为优选技术方案， 本发明所述树脂组合物由组成物和溶剂组成； 所述组 成物按重量份数包括如下组分：
无卤环氧树脂： 20〜100份； As a preferred technical solution, the resin composition of the present invention is composed of a composition and a solvent; the composition includes the following components in parts by weight: Halogen-free epoxy resin: 20~100 parts;
腈基树脂： 10〜30份； Nitrile-based resin: 10 to 30 parts;
烯丙基改性双马树脂预聚体： 20〜100份； Allyl modified bismale resin prepolymer: 20~100 parts;
固化剂： 20〜100份； Curing agent: 20~100 parts;
填料： 10〜100份； Filler: 10~100 parts;
固化促进剂： 0.01〜1.0份; Curing accelerator: 0.01~1.0 parts;
其中，组成物溶于溶剂，并且组成物占总重的重量百分比为 65%〜75%之间。 当然， 本发明还可根据需要添加着色颜料、 消泡剂、 表面活性剂、 阻燃剂、 紫外吸收剂、 抗氧剂、 流动调整剂等公知的添加剂， 所述添加剂的种类和添加 量本发明不做具体限定， 本领域技术人员可以根据掌握的专业知识进行选择。 Wherein the composition is dissolved in a solvent, and the weight percentage of the composition in the total weight is between 65% and 75%. Of course, the present invention may also add a known additive such as a coloring pigment, an antifoaming agent, a surfactant, a flame retardant, an ultraviolet absorber, an antioxidant, a flow regulator, etc., as needed, the type and amount of the additive. Without specific limitation, those skilled in the art can make a selection based on the expertise acquired.
本发明所述的热固性树脂组合物的制备方法， 本领域技术人员可以参考现 有的树脂组合物的制备方法， 结合实际情况进行选择， 本发明不做特殊限定。 典型但非限制性的热固性树脂组合物的制备方法包括如下步骤： The preparation method of the thermosetting resin composition of the present invention can be selected by those skilled in the art with reference to the preparation method of the existing resin composition, and the actual situation is selected, and the present invention is not particularly limited. A typical but non-limiting method of preparing a thermosetting resin composition includes the following steps:
取配方量的环氧树脂、 腈基树脂、 烯丙基改性双马树脂预聚体、 固化剂、 填料、 固化促进剂加入反应容器或反应釜中， 加入配方量的溶剂， 搅拌均匀得 到固含量在 65〜75 %的胶液， 即为热固性树脂组合物的胶液； The formulation amount of the epoxy resin, the nitrile resin, the allyl modified buma resin prepolymer, the curing agent, the filler, the curing accelerator are added to the reaction vessel or the reaction kettle, and the solvent of the formula amount is added, and the mixture is uniformly stirred to obtain a solid. a glue solution having a content of 65 to 75%, that is, a glue solution of a thermosetting resin composition;
其中， 所述烯丙基改性双马树脂预聚体的制备方法为： 将双马来酰亚胺树 脂和二烯丙基化合物按 100: ( 15〜120 ) 的质量混合， 并在 110〜160°C下反应 30〜120min， 得到烯丙基改性双马树脂预聚体。 Wherein, the allyl modified bismale resin prepolymer is prepared by: mixing a bismaleimide resin and a diallyl compound by a mass of 100: (15~120), and at 110~ The reaction was carried out at 160 ° C for 30 to 120 min to obtain an allyl modified bismale resin prepolymer.
本发明目的之二所述的半固化片， 由增强材料及浸润于增强材料上的基体 材料组成， 所述基体材料为目的之一所述的热固性树脂组合物。 The prepreg according to the second aspect of the present invention comprises a reinforcing material and a base material impregnated on the reinforcing material, wherein the base material is a thermosetting resin composition according to any one of the objectives.
半固化片又称 "PP片"或"粘结片"， 是增强材料浸渍上树脂胶液， 再经热 处理预烘， 制成的薄片材料。 所述半固化片在加热加压下会软化， 冷却后会反
应固化。 The prepreg, also known as "PP sheet" or "bonding sheet", is a sheet material prepared by impregnating a resin glue with a reinforcing material and pre-baking it by heat treatment. The prepreg will soften under heat and pressure, and will be reversed after cooling. Should be cured.
本发明所述的基料为无机或有机材料。 The binder of the present invention is an inorganic or organic material.
所述无机材料选自玻璃纤维、 碳纤维、 硼纤维、 金属的机织织物或无纺布。 所述玻璃纤维布或无纺布选自 E-glass、 Q型布、 NE布、 D型布、 S型布、 高硅 氧布中的任意 1种； 所述玻璃纤维布优选 E-glass。 The inorganic material is selected from the group consisting of glass fibers, carbon fibers, boron fibers, metal woven fabrics, or nonwoven fabrics. The glass fiber cloth or nonwoven fabric is selected from any one of E-glass, Q-type cloth, NE cloth, D-type cloth, S-type cloth, and high-silicone cloth; and the glass fiber cloth is preferably E-glass.
所述有机材料选自聚酯、 聚胺、 聚丙烯酸、 聚酰亚胺、 芳纶、 聚四氟乙烯、 或间规聚苯乙烯制造的织布或无纺布或无纺纸。 The organic material is selected from the group consisting of polyester, polyamine, polyacrylic acid, polyimide, aramid, polytetrafluoroethylene, or syndiotactic polystyrene woven or nonwoven or nonwoven paper.
本发明所述半固化片的制备方法， 本领域技术人员可以参考现有的半固化 片的制备方法， 本发明不做具体限定， 典型但非限制性的所述半固化片的制备 方法包括如下步骤： For the preparation method of the prepreg according to the present invention, those skilled in the art can refer to the preparation method of the existing prepreg, which is not specifically limited. The typical but non-limiting preparation method of the prepreg includes the following steps:
选取表面平整的基料 （如 E-玻纤布）， 均匀涂覆热固性树脂组合物的胶液， 然后进行烘制， 使其中的热固性树脂组合物处于半固化阶段 （B-stage) , 即得粘 其中， 所述烘制的温度依据热固性树脂组合物胶液所采用的溶剂的沸点来 选择， 一般为大于溶剂沸点的 20〜80°C， 优选 80〜250°C， 所述烘制的时间为 l〜30min。 Selecting a flat-surfaced base material (such as E-glass cloth), uniformly coating the glue of the thermosetting resin composition, and then baking, so that the thermosetting resin composition therein is in a semi-curing stage (B-stage), that is, The temperature of the baking is selected according to the boiling point of the solvent used for the thermosetting resin composition glue, generally 20 to 80 ° C, preferably 80 to 250 ° C, which is greater than the boiling point of the solvent, and the baking time. For l~30min.
本发明提供的半固化片具备良好的机械加工性， 可实现无卤阻燃， 且具有 优良的耐湿热性和耐热性、 低热膨胀系数及低介电常数和介电损耗等特性。 本发明目的之三所述的印制电路用覆金属箔层压板， 包括层压板及压覆于 层压板的一侧或两侧的金属箔， 所述层压板包括数片相贴合的目的之二所述的 半固化片， 所述半固化片由增强材料及浸润于增强材料上的基体材料组成， 所 述基体材料为目的之一所述的热固性树脂组合物。
层压板是层压制品的一种， 是由两层或多层浸有树脂的纤维或织物 （即预 浸料）， 经叠合、 热压结合成的整体。 印制电路用覆金属箔层压板是在普通层压 板的单面或双面的覆金属箔得到的。 The prepreg provided by the invention has good machinability, can realize halogen-free flame retardancy, and has excellent heat and humidity resistance, heat resistance, low thermal expansion coefficient, low dielectric constant and dielectric loss. A metal foil-clad laminate for a printed circuit according to the third aspect of the present invention, comprising a laminate and a metal foil laminated on one side or both sides of the laminate, the laminate comprising a plurality of sheets for the purpose of bonding In the prepreg according to the second aspect, the prepreg is composed of a reinforcing material and a base material impregnated on the reinforcing material, and the base material is a thermosetting resin composition according to any one of the objectives. A laminate is a type of laminate which is a composite of two or more layers of resin-impregnated fibers or fabrics (i.e., prepregs) which are laminated and heat-pressed. The metal foil-clad laminate for printed circuit boards is obtained on a single-sided or double-sided metal foil of a conventional laminate.
优选地， 本发明所述金属箔为铜箔 Preferably, the metal foil of the present invention is a copper foil
本发明所述印制电路用层压板的制备方法， 本领域技术人员可以参考现有 的覆铜箔层压板的制备方法， 本发明不做具体限定， 典型但非限制性的所述印 制电路用覆金属箔层压板的制备方法包括如下步骤： The method for preparing a laminate for a printed circuit according to the present invention, those skilled in the art can refer to the preparation method of the existing copper-clad laminate, which is not specifically limited in the present invention, and the printed circuit is typically but not limited. The preparation method of the metal foil-clad laminate comprises the following steps:
裁切半固化片至相应尺寸， 并将数张裁切后的半固化片整齐叠加； 然后在 相叠合的半固化片的上侧和 /或下侧叠合一张铜箔； 最后将叠合好的覆铜箔的半 固化片进行热压成型压制， 制得印制电路用层压板。 Cutting the prepreg to the corresponding size, and stacking the plurality of cut prepregs neatly; then laminating a copper foil on the upper side and/or the lower side of the laminated prepreg; and finally laminating the copper foil The prepreg is subjected to hot press molding to obtain a laminate for a printed circuit.
其中热压成型在层压设备中进行， 热压成型优选采用阶梯式压制法 （即分 步升温及升压法） 进行压制。 所述阶梯式压制法的具体操作条件优选为： Among them, hot press forming is carried out in a laminating apparatus, and hot press forming is preferably carried out by a stepwise pressing method (i.e., stepwise heating and pressure increasing). The specific operating conditions of the stepwise pressing method are preferably:
温度梯度为① 15min内从室温升至 150°C， 保持 30min; ②在 5min内升至 180°C保持 2h; ③ 30min降温至室温； The temperature gradient was raised from room temperature to 150 ° C in 1 15 min for 30 min; 2 was raised to 180 ° C for 5 h in 5 min; 3 30 min was cooled to room temperature;
压力梯度为① lmin内从零升至 0.6MPa，保压 30min;② lmin内升至 l .OMPa, 保压 2.5h; The pressure gradient is from 0 to 0.6 MPa in 1 lmin, and the pressure is maintained for 30 min; in 2 lmin, it rises to l.OMPa, and the pressure is 2.5 h ;
后处理条件为 200〜245 °C保持 1〜5小时。 The post-treatment conditions are maintained at 200~245 °C for 1 to 5 hours.
本发明提供的覆铜箔层压板具备良好的机械加工性， 可实现无卤阻燃， 且 具有优良的耐湿热性和耐热性、 低热膨胀系数及低介电常数和介电损耗等特性。 与现有技术相比， 本发明具有如下有益效果： The copper-clad laminate provided by the present invention has good machinability, can achieve halogen-free flame retardancy, and has excellent heat and heat resistance, low thermal expansion coefficient, low dielectric constant and dielectric loss. Compared with the prior art, the present invention has the following beneficial effects:
( 1 ) 本发明所述的热固性树脂组合物以烯丙基改性双马树脂预聚体、 腈基 树脂和无^环氧树脂为主要成分， 通过丙烯基化合物对双马来酰亚胺树脂的改
性， 提高了热固性树脂的韧性及溶解性； 通过腈基树脂的加入， 提高了热固性 树脂组合物的阻燃性， 耐热性和低介电性， 进而获得了 UL-V0水平的印制电路 用层压板； 而无卤环氧树脂的加入进一步改善了热固性树脂组合物的韧性和机 械加工性； (1) The thermosetting resin composition of the present invention contains an allyl-modified bismale resin prepolymer, a nitrile-based resin, and a non-epoxy resin as a main component, and a bismaleimide resin is used as a main component. Change Improves the toughness and solubility of the thermosetting resin. By adding nitrile-based resin, the flame retardancy, heat resistance and low dielectric property of the thermosetting resin composition are improved, and a printed circuit of UL-V0 level is obtained. Using a laminate; and the addition of a halogen-free epoxy resin further improves the toughness and machinability of the thermosetting resin composition;
(2) 本发明提供的半固化片、 印制电路用层压板具备良好的机械加工性， 可实现无卤阻燃， 且具有优良的耐湿热性和耐热性、 低热膨胀系数及低介电常 数和介电损耗等特性。 (2) The prepreg and the printed circuit board provided by the present invention have good machinability, can realize halogen-free flame retardancy, and have excellent heat and heat resistance, low thermal expansion coefficient, and low dielectric constant. Characteristics such as dielectric loss.
具体实施方式 detailed description
为更好地说明本发明， 便于理解本发明的技术方案， 本发明的典型但非限 制性的实施例如下： In order to better explain the present invention, it is convenient to understand the technical solution of the present invention, and a typical but non-limiting embodiment of the present invention is as follows:
在所述实施例和对比例中， 如无特别说明， 其份代表重量份， 其％代表"重 量％"。 合成例 1 In the examples and comparative examples, unless otherwise stated, the parts represent parts by weight, and the % represents "% by weight". Synthesis example 1
一种烯丙基改性双马树脂预聚体， 通过如下方法制备得到： An allyl modified bismale resin prepolymer prepared by the following method:
将 4,4'-二苯甲烷双马来酰亚胺树脂和二烯丙基双酚 A按照 100:30的质量比 混合， 并在 110°C下反应 20min， 得到烯丙基改性双马树脂预聚体， 记为双马 1。 The 4,4'-diphenylmethane bismaleimide resin and diallyl bisphenol A were mixed at a mass ratio of 100:30, and reacted at 110 ° C for 20 min to obtain an allyl modified double horse. Resin prepolymer, recorded as double horse 1.
合成例 2 Synthesis Example 2
一种烯丙基改性双马树脂预聚体， 通过如下方法制备得到： An allyl modified bismale resin prepolymer prepared by the following method:
将 4,4'-二苯异丙基双马来酰亚胺树脂和烯丙基酚氧树脂按照 100:120 的质 量比混合， 并在 160°C下反应 30min， 得到烯丙基改性双马树脂预聚体， 即为双 合成例 3
一种烯丙基改性双马树脂预聚体， 通过如下方法制备得到： 4,4'-diphenylisopropyl bismaleimide resin and allyl phenoxy resin were mixed at a mass ratio of 100:120, and reacted at 160 ° C for 30 min to obtain an allyl modified double Horse resin prepolymer, which is double synthesis example 3 An allyl modified bismale resin prepolymer prepared by the following method:
将 4,4'-二苯砜双马来酰亚胺树脂和二烯丙基二苯醚按照 100: 15的质量比混 合， 并在 120°C下反应 120min， 得到烯丙基改性双马树脂预聚体， 即为双马 3。 The 4,4'-diphenyl sulfone bismaleimide resin and diallyl diphenyl ether were mixed at a mass ratio of 100:15 and reacted at 120 ° C for 120 min to obtain an allyl modified double horse. Resin prepolymer, which is double horse 3.
实施例 1〜11提供了 11种热固性树脂组合物； 对比例 1〜7提供了 7种树脂 组合物， 用于与实施例 1〜11提供的树脂组合物进行比较； 所述实施例 1〜6提供 的树脂组合物的配方见表 1， 所述实施例 7〜11提供的树脂组合物的配方见表 2; 所述对比例 1〜7提供的树脂组合物的配方见表 3。 Examples 1 to 11 provided 11 kinds of thermosetting resin compositions; Comparative Examples 1 to 7 provided 7 kinds of resin compositions for comparison with the resin compositions provided in Examples 1 to 11; the examples 1 to 6 The formulations of the resin compositions provided are shown in Table 1. The formulations of the resin compositions provided in Examples 7 to 11 are shown in Table 2; and the formulations of the resin compositions provided in Comparative Examples 1 to 7 are shown in Table 3.
表 1 实施例 1〜6提供的树脂组合物的配方 Table 1 Formulations of the resin compositions provided in Examples 1 to 6
氢氧化铝 10 10 10 10 10 10 二氧化硅 10 10 10 10 10 10 氢氧化镁 10 10 10 10 10 10 甲氧基硅烷偶联剂 Aluminum hydroxide 10 10 10 10 10 10 Silica 10 10 10 10 10 10 Magnesium hydroxide 10 10 10 10 10 10 methoxysilane coupling agent
2-甲基咪唑 0.10 0.15 0.15 0.15 0.20 0.20 丁酮 适量 适量 适量 适量 适量 适量 丙二醇甲醚 适量 适量 适量 适量 适量 适量 固含量 65% 65% 65% 65% 65% 65% 表 2 实施例 7〜11提供的树脂组合物的配方 2-methylimidazole 0.10 0.15 0.15 0.15 0.20 0.20 Butanone Appropriate amount appropriate amount appropriate amount appropriate amount of propylene glycol methyl ether proper amount appropriate amount appropriate amount appropriate amount solid content 65% 65% 65% 65% 65% 65% Table 2 Examples 7~11 provide Formula of resin composition
二氨基二苯砜 8 一 一 一 一 含氮酚醛 一 一 10 20 20 氢氧化铝 10 10 5 10 40 二氧化硅 10 10 5 10 30 氢氧化镁 10 10 0 10 30 甲氧基硅烷偶联剂 一 0.5 0.5 0.5 0.5 Diaminodiphenyl sulfone 8 1-1 one nitrogen phenol aldehyde one 10 20 20 aluminum hydroxide 10 10 5 10 40 silica 10 10 5 10 30 magnesium hydroxide 10 10 0 10 30 methoxy silane coupling agent 0.5 0.5 0.5 0.5
2-甲基咪唑 0.20 0.10 0.10 0.10 0.10 丁酮 适量 适量 适量 适量 适量 丙二醇甲醚 适量 适量 适量 适量 适量 固含量 65% 65% 65% 65% 75% 表 3 对比例 1〜7提供的树脂组合物的配方 2-methylimidazole 0.20 0.10 0.10 0.10 0.10 Butanone Appropriate amount Appropriate amount Appropriate amount of propylene glycol methyl ether Appropriate amount Appropriate amount Appropriate amount Solid content 65% 65% 65% 65% 75% Table 3 Comparative Example 1 to 7 provided resin composition Formula
8 8 8 8 8 8 8 砜 含氮酚醛 一 10 氢氧化铝 10 10 10 10 10 10 10 二氧化硅 10 10 10 10 10 10 10 氢氧化镁 10 10 10 10 10 10 10 甲氧基硅烷偶联剂 8 8 8 8 8 8 8 Sulfone nitrogen-containing phenolic- 10 Aluminium hydroxide 10 10 10 10 10 10 10 Silica 10 10 10 10 10 10 10 Magnesium hydroxide 10 10 10 10 10 10 10 Methoxysilane coupling agent
2-甲基咪唑 0.20 0.20 0.15 0.15 0.15 0.15 0.15 丁酮 适量 适量 适量 适量 适量 适量 适量 丙二醇甲醚 适量 适量 适量 适量 适量 适量 适量 固含量 65% 65% 65% 65% 65% 65% 65% 其中， 双酚 A为双酚 A型环氧树脂， 豪斯麦 Huntsman的 8093， 环氧当量 2-methylimidazole 0.20 0.20 0.15 0.15 0.15 0.15 0.15 Butane ketone right amount appropriate amount appropriate amount appropriate amount of propylene glycol methyl ether proper amount appropriate amount appropriate amount appropriate amount of solid content 65% 65% 65% 65% 65% 65% 65% of which Phenol A is bisphenol A type epoxy resin, Haussman Huntsman's 8093, epoxy equivalent
480g/mol; 480g/mol ;
DCPD为双环戊二烯环氧树脂，日本 DIC的 HP-7200H,环氧当量 890g/mol; 联苯型为联苯型环氧树脂， SHIN-A的 SE-5000, 环氧当量 256g/mol; 双酚 F为双酚 F环氧树脂， 上海势越的 KF21 , 环氧当量 542g/mol;
腈基树脂参照 CN102976972所述腈基树脂单体 （即含苯并恶嗪环的四邻苯 二甲腈树脂单体） 的方法制备得到， 具体结构为： DCPD is dicyclopentadiene epoxy resin, Japan DIC HP-7200H, epoxy equivalent 890g / mol; biphenyl type is biphenyl type epoxy resin, SHIN-A SE-5000, epoxy equivalent 256g / mol; Bisphenol F is bisphenol F epoxy resin, Shanghai Shi Yue KF21, epoxy equivalent 542g / mol; The nitrile-based resin is prepared by the method of the nitrile-based resin monomer (ie, the tetraphthalamide resin monomer containing a benzoxazine ring) described in CN102976972, and the specific structure is as follows:
双马 2为合成例 2得到的烯丙基改性双马树脂预聚体； Double horse 2 is the allyl modified bismale resin prepolymer obtained in Synthesis Example 2;
双马 3为合成例 3得到的烯丙基改性双马树脂预聚体； Double horse 3 is the allyl modified bismale resin prepolymer obtained in Synthesis Example 3;
双氰胺， 购自宁夏大荣； Dicyandiamide, purchased from Ningxia Darong;
线性酚醛， 为购自韩国 MOMENTIVE的 2812， 羟基当量 105g/mol; Linear novolac, is 2812 purchased from Korea MOMENTIVE, hydroxyl equivalent 105g / mol ;
二氨基二苯砜， 购自台湾六和化工股份； Diaminodiphenyl sulfone, purchased from Taiwan Liuhe Chemical Co., Ltd.;
含氮酚醛为购自晋一化工的 A-125, 羟基当量为 125g/mol; The nitrogen-containing phenolic aldehyde is A-125 purchased from Jinyi Chemical Co., with a hydroxyl equivalent of 125 g/mol ;
氢氧化铝， 平均料径为 1〜5μηι， 纯度 99%以上； Aluminum hydroxide, the average material diameter is 1~5μηι, and the purity is more than 99%;
二氧化硅， 平均料径为 1〜3μηι， 纯度 99%以上； Silica, the average material diameter is 1~3μηι, and the purity is 99% or more;
氢氧化镁， 平均料径为 1〜3μηι， 纯度 99%以上； Magnesium hydroxide, the average material diameter is 1~3μηι, and the purity is more than 99%;
2-甲基咪唑， 购自巴斯夫； 2-methylimidazole, purchased from BASF;
丁酮， 化学纯； Butanone, chemically pure;
丙二醇甲醚， 化学纯。 Propylene glycol methyl ether, chemically pure.
实施例 1〜11和对比例 1〜7提供的树脂组合物的制备方法为： The preparation methods of the resin compositions provided in Examples 1 to 11 and Comparative Examples 1 to 7 were as follows:
将配方量的各组分混合加入反应釜中， 并用丁酮稀释至指定固含量， 搅拌
均匀得到热固性树脂组合物的胶液。 Mixing the components of the formula into the reaction kettle, diluting with methyl ethyl ketone to the specified solids, stirring The glue of the thermosetting resin composition was uniformly obtained.
在对比例 2 中， 由于保证固化效果的原因， 所以添加了固化剂含氮酚醛， 该固化剂对于性能测试的结果没有影响。 性能测试： In Comparative Example 2, since the curing effect was ensured, the curing agent nitrogen-containing phenolic aldehyde was added, and the curing agent had no effect on the results of the performance test. Performance Testing:
将实施例 1〜11和对比例 1〜7提供的树脂组合物， 按照如下方法制备覆金属 箔层压板， 并对制备得到的覆金属箔层压板进行性能测试。 The resin compositions provided in Examples 1 to 11 and Comparative Examples 1 to 7 were prepared as follows, and a metal foil-clad laminate was prepared as follows, and the prepared metal foil-clad laminate was subjected to performance test.
所述热固化片的制备方法包括： The preparation method of the thermosetting sheet includes:
将热固性树脂组合物的胶液含浸玻璃纤维布， 并进行叠加获得叠层的含浸 胶液的玻璃纤维布， 之后于 250°C下加热、 加压 3h， 得到热固性树脂组合物复 合材料。 性能测试的项目及具体方法为： The glue of the thermosetting resin composition was impregnated with a glass fiber cloth, and laminated to obtain a laminated glass cloth containing a dipping liquid, followed by heating and pressurizing at 250 ° C for 3 hours to obtain a thermosetting resin composition composite material. The performance test items and specific methods are:
( 1 ) 玻璃化转变温度 （Tg): (1) Glass transition temperature (Tg):
根据差示扫描量热法， 按照 IPC-TM-650中 2.4.25所规定的 DSC方法进行 According to the differential scanning calorimetry method, according to the DSC method specified in 2.4.25 of IPC-TM-650
(2) 剥离强度： (2) Peel strength:
按照 IPC-TM-650中 2.4.8所规定的方法中 "热应力" 的实验条件， 测试金 属盖层的剥离强度。 The peel strength of the metal cap layer was tested in accordance with the experimental conditions of "thermal stress" in the method specified in 2.4.8 of IPC-TM-650.
(3 ) 燃烧性： (3) Flammability:
依据 UL94法垂直燃烧法测定。 Determined according to the UL94 method vertical burning method.
(4) 热分层时间 T-288: (4) Thermal stratification time T-288:
按照 IPC-TM-650中 2.4.24.1所规定的方法进行测定。
(5 ) 热膨胀系数 Z轴 CTE (TMA): The measurement was carried out in accordance with the method specified in 2.4.24.1 of IPC-TM-650. (5) Thermal expansion coefficient Z-axis CTE (TMA):
按照 IPC-TM-650中 2.4.24所规定的方法进行测定。 The measurement was carried out in accordance with the method specified in 2.4.24 of IPC-TM-650.
(6) 热分解温度 Td: (6) Thermal decomposition temperature Td:
按照 IPC-TM-650中 2.4.26规定的方法进行测定。 The measurement was carried out in accordance with the method specified in 2.4.26 of IPC-TM-650.
(7) 吸水性： (7) Water absorption:
按照 IPC-TM-650中的 2.6.2.1所规定的方法进行测定。 The measurement was carried out in accordance with the method specified in 2.6.2.1 of IPC-TM-650.
(8 ) 介质损耗角正切： (8) Dielectric loss tangent:
根据使用条状线的共振法， 按照 IPC-TM-650 中 2.5.5.9 规定的方法测定 According to the resonance method using the strip line, it is determined according to the method specified in 2.5.5.9 of IPC-TM-650.
1GHz下的介质损耗角正切。 Dielectric loss tangent at 1 GHz.
(9) 冲孔性 (9) Punching
将 1.6mm厚的基材放于冲模器上进行冲孔， 以肉眼观察孔边情况： （1^ )孔 边无白圈， 用符号〇表示； （h2) 空边有白圈， 用符号 Δ表示； （h3) 孔边开裂， 用符号 X表示。 Place a 1.6mm thick substrate on the die to punch the hole, and observe the hole edge with the naked eye: (1^) There is no white circle on the hole edge, denoted by the symbol ;; (h 2 ) The white edge has a white circle, with the symbol Δ indicates; (h 3 ) the edge of the hole is cracked, indicated by the symbol X.
( 10) 卤素含量 (10) Halogen content
按照 IPC-TM-650中 2.3.41的方法进行测定。 The measurement was carried out in accordance with the method of 2.3.41 of IPC-TM-650.
由实施例 1〜6提供的树脂组合物制备的热固化片的性能测试结果如表 4所 示； 由实施例 7〜11提供的树脂组合物制备的热固化片的性能测试结果如表 5所 示； 由对比例 1〜7提供的树脂组合物制备的热固化片的性能测试结果如表 6所 The results of the performance test of the thermosetting sheets prepared from the resin compositions provided in Examples 1 to 6 are shown in Table 4; the results of the performance test of the thermosetting sheets prepared from the resin compositions provided in Examples 7 to 11 are shown in Table 5. The performance test results of the thermosetting sheets prepared from the resin compositions provided in Comparative Examples 1 to 7 are shown in Table 6.
4 实施例 1〜6提供的树脂组合物制备的热固化片的性能测试结果
玻璃化转变温度 Tg ( °c ) 175 180 185 200 190 183 剥离强度 （N/mm) 1.66 1.72 1.70 1.83 1.89 1.76 燃烧性 （UL94) V-0 V-0 V-0 V-0 V-0 V-0 热分层时间 （min) >60 >60 >60 >60 >60 >60 热膨胀系数 Z轴 CTE 2.9 2.6 2.7 2.5 2.4 2.4 (TMA) (30-260°C ) % 4 Performance test results of the thermosetting sheet prepared by the resin compositions provided in Examples 1 to 6 Glass transition temperature Tg ( °c ) 175 180 185 200 190 183 Peel strength (N/mm) 1.66 1.72 1.70 1.83 1.89 1.76 Flammability (UL94) V-0 V-0 V-0 V-0 V-0 V- 0 Thermal stratification time (min) >60 >60 >60 >60 >60 >60 Thermal expansion coefficient Z-axis CTE 2.9 2.6 2.7 2.5 2.4 2.4 (TMA) (30-260°C) %
热分解温度 Td (TGA， °C ) 398 411 405 414 416 405 吸水性 （％) 0.1 0.1 0.11 0.1 0.13 0.1 介质损耗角正切 0.007 0.006 0.008 0.007 0.009 0.007 ( 1GHz) Thermal decomposition temperature Td (TGA, °C) 398 411 405 414 416 405 Water absorption (%) 0.1 0.1 0.11 0.1 0.13 0.1 Dielectric loss tangent 0.007 0.006 0.008 0.007 0.009 0.007 ( 1GHz)
冲孔性 〇 〇 〇 〇 〇 〇 卤素含量 （C1) 0.04 0.03 0.05 0.04 0.04 0.04 卤素含量 （Br) 0 0 0 0 0 0 表 5 实施例 7〜11提供的树脂组合物制备的热固化片的性能测试结果 项目 实施例 Punching enthalpy halogen content (C1) 0.04 0.03 0.05 0.04 0.04 0.04 Halogen content (Br) 0 0 0 0 0 0 Table 5 Properties of thermosetting sheets prepared by the resin compositions provided in Examples 7 to 11 Test result project example
7 8 9 10 11 玻璃化转变温度 Tg ( °c ) 200 175 170 195 175 剥离强度 （N/mm) 1.70 1.80 1.60 1.90 1.60 燃烧性 （UL94) V-0 V-0 V-0 V-1 V-0 热分层时间 （min) >60 >60 >60 >60 >60 热膨胀系数 Z轴 CTE 2.5 2.9 2.7 2.8 2.3 (TMA) (30-260°C ) %
热分解温度 Td (TGA， °C ) 410 398 391 400 400 吸水性 （％) 0.15 0.1 0.1 0.1 0.1 介质损耗角正切 0.008 0.007 0.006 0.007 0.006 ( 1GHz) 7 8 9 10 11 Glass transition temperature Tg ( °c ) 200 175 170 195 175 Peel strength (N/mm) 1.70 1.80 1.60 1.90 1.60 Flammability (UL94) V-0 V-0 V-0 V-1 V- 0 Thermal stratification time (min) >60 >60 >60 >60 >60 Thermal expansion coefficient Z-axis CTE 2.5 2.9 2.7 2.8 2.3 (TMA) (30-260°C) % Thermal decomposition temperature Td (TGA, °C) 410 398 391 400 400 Water absorption (%) 0.15 0.1 0.1 0.1 0.1 Dielectric loss tangent 0.008 0.007 0.006 0.007 0.006 ( 1 GHz)
冲孔性 〇 〇 〇 △ 〇 卤素含量 （C1) 0.04 0.04 0.04 0.05 0.04 卤素含量 （Br) 0 0 0 0 0 Punching 〇 〇 △ △ 卤素 Halogen content (C1) 0.04 0.04 0.04 0.05 0.04 Halogen content (Br) 0 0 0 0 0
表 6 对比例提供的树脂组合物制备的热固化片的性能测试结果 项目 对比例 Table 6 Performance test results of the thermosetting sheet prepared from the resin composition provided in the comparative example Item Comparative Example
1 2 3 4 5 6 7 玻璃化转变温度 Tg ( °c ) 191 170 180 175 190 175 180 剥离强度 （N/mm) 1.64 1.58 1.51 1.80 1.69 1.85 1.86 燃烧性 （UL94 ) V-0 V-0 V-0 V-0 V-0 V-0 V-0 热分层时间 （min) 5 3 >60 >60 >60 >60 >60 热膨胀系数 Z轴 CTE (TMA) 3.0 3.1 2.7 2.8 2.5 2.3 2.8 (30-260 °C ) % 1 2 3 4 5 6 7 Glass transition temperature Tg ( °c ) 191 170 180 175 190 175 180 Peel strength (N/mm) 1.64 1.58 1.51 1.80 1.69 1.85 1.86 Flammability (UL94) V-0 V-0 V- 0 V-0 V-0 V-0 V-0 Thermal stratification time (min) 5 3 >60 >60 >60 >60 >60 Thermal expansion coefficient Z-axis CTE (TMA) 3.0 3.1 2.7 2.8 2.5 2.3 2.8 (30- 260 °C ) %
热分解温度 Td (TGA， °C ) 381 390 384 390 415 410 405 吸水性 （％) 0.1 0.12 0.20 0.21 0.3 0.1 0.13 介质损耗角正切 （1GHz) 0.010 0.011 0.010 0.012 0.006 0.009 0.010 冲孔性 △ △ 〇 △ 〇 〇 〇 卤素含量 C1 0.05 0.04 0.04 0.04 0.04 0.04 0.04 Thermal decomposition temperature Td (TGA, °C) 381 390 384 390 415 410 405 Water absorption (%) 0.1 0.12 0.20 0.21 0.3 0.1 0.13 Dielectric loss tangent (1 GHz) 0.010 0.011 0.010 0.012 0.006 0.009 0.010 Punchability △ △ 〇 △ 〇〇〇Halogen content C1 0.05 0.04 0.04 0.04 0.04 0.04 0.04
Br 0 0 0 0 0 0 0
从测试结果可以看出， 本发明所述的热固性树脂组合物以烯丙基改性双马 树脂预聚体、 腈基树脂和无 ^环氧树脂为主要成分， 通过丙烯基化合物对双马 来酰亚胺树脂的改性， 提高了热固性树脂的韧性及溶解性； 通过腈基树脂的加 入，提高了热固性树脂组合物的阻燃性，耐热性和低介电性，进而获得了 UL-V0 水平的印制电路用层压板； 而无卤环氧树脂的加入进一步改善了热固性树脂组 合物的韧性和机械加工性。 另外， 本发明的树脂组合物不含卤素和磷元素， 阻 燃性达到 UL94-V0级； 由其得到的半固化片和覆铜箔层压板， 具有高耐热、 高 可靠性、 高玻璃化转变温度 （Tg)、 难燃性、 低吸水率、 低介电损耗及低膨胀系 数， 并具有良好的加工性能。 Br 0 0 0 0 0 0 0 It can be seen from the test results that the thermosetting resin composition of the present invention mainly comprises an allyl-modified bismale resin prepolymer, a nitrile-based resin and an epoxy-free epoxy resin, and a propylene-based compound to the double-malay The modification of the imide resin improves the toughness and solubility of the thermosetting resin; the addition of the nitrile-based resin improves the flame retardancy, heat resistance and low dielectric property of the thermosetting resin composition, thereby obtaining UL- A laminate for printed circuit of V0 level; and the addition of a halogen-free epoxy resin further improves the toughness and machinability of the thermosetting resin composition. In addition, the resin composition of the present invention contains no halogen and phosphorus, and has a flame retardancy of UL94-V0 grade; a prepreg and a copper-clad laminate obtained therefrom have high heat resistance, high reliability, and high glass transition temperature. (Tg), flame retardancy, low water absorption, low dielectric loss and low expansion coefficient, and good processing properties.
应该注意到并理解， 在不脱离后附的权利要求所要求的本发明的精神和范 围的情况下， 能够对上述详细描述的本发明做出各种修改和改进。 因此， 要求 保护的技术方案的范围不受所给出的任何特定示范教导的限制。 It will be appreciated and appreciated that various modifications and improvements can be made to the invention described in the Detailed Description without departing from the spirit and scope of the invention. Therefore, the scope of the claimed technical solutions is not limited by any particular exemplary teachings presented.
申请人声明， 本发明通过上述实施例来说明本发明的详细方法， 但本发明 并不局限于上述详细方法， 即不意味着本发明必须依赖上述详细方法才能实施。 所属技术领域的技术人员应该明了， 对本发明的任何改进， 对本发明产品各原 料的等效替换及辅助成分的添加、 具体方式的选择等， 均落在本发明的保护范 围和公开范围之内。
The Applicant claims that the present invention is described by the above-described embodiments, but the present invention is not limited to the above detailed methods, that is, it does not mean that the present invention must be implemented by the above detailed methods. It will be apparent to those skilled in the art that any modifications of the present invention, equivalent substitution of the various materials of the product of the present invention, addition of auxiliary components, selection of specific means, and the like, are all within the scope of the present invention.
Claims
1、 一种热固性树脂组合物， 其特征在于， 所述树脂组合物由组成物和溶剂 组成； 所述组成物按重量份数包括如下组分： 1. A thermosetting resin composition, characterized in that the resin composition consists of a composition and a solvent; the composition includes the following components in parts by weight:
无卤环氧 20〜100份； Halogen-free epoxy 20~100 parts;
腈基树脂： 10〜30份； Nitrile-based resin: 10~30 parts;
烯丙基改性双马树脂预聚体： 20〜100份； Allyl modified bismuth resin prepolymer: 20~100 parts;
固化剂： 20〜100份； Curing agent: 20~100 parts;
填料： 10〜100份； Filling: 10~100 parts;
其中，组成物溶于溶剂，并且组成物占总重的重量百分比为 65〜75wt%之间。 Wherein, the composition is dissolved in the solvent, and the weight percentage of the composition to the total weight is between 65 and 75 wt%.
2、如权利要求 1所述的组合物，其特征在于，所述无卤环氧树脂的结构为:
2. The composition of claim 1, wherein the structure of the halogen-free epoxy resin is:
其中， Ar1选自如下结构中的任意 1种: Among them, Ar 1 is selected from any one of the following structures:
优选地， 所述无卤环氧树脂的环氧当量为 200〜2000。 Preferably, the epoxy equivalent of the halogen-free epoxy resin is 200~2000.
3、 如权利要求 1或 2所述的组合物， 其特征在于， 所述腈基树脂为含有
个腈基的高分子体， 其结构式为： 3. The composition of claim 1 or 2, wherein the nitrile resin contains A nitrile-based polymer, its structural formula is:
其中， Ar2选自如下结构中的任意 1种： Among them, Ar 2 is selected from any one of the following structures:
、
,
4、 如权利要求 1〜3之一所述的组合物， 其特征在于， 所述烯丙基改性双马 树脂预聚体为双马来酰亚胺树脂经二烯丙基化合物改性得到的； 所述改性的反 应温度为 110〜160°C， 改性的反应时间为 20〜120min; 其中， 双马来酰亚胺树脂 和二烯丙基化合物的质量比优选为 100: ( 15〜120); 4. The composition according to one of claims 1 to 3, characterized in that the allyl-modified bismale resin prepolymer is a bismaleimide resin modified by a diallyl compound. ; The reaction temperature of the modification is 110~160°C, and the reaction time of the modification is 20~120min ; wherein, the mass ratio of the bismaleimide resin and the diallyl compound is preferably 100: (15 ~120) ;
优选地，所述双马来酰亚胺树脂选自 4,4'-二苯甲烷双马来酰亚胺树脂、4,4'- 二苯醚双马来酰亚胺树脂、 4,4'-二苯异丙基双马来酰亚胺树脂、 4,4'-二苯砜双马 来酰亚胺树脂中的任意 1种或至少 2种的组合； Preferably, the bismaleimide resin is selected from the group consisting of 4,4'-diphenylmethane bismaleimide resin, 4,4'-diphenyl ether bismaleimide resin, and 4,4'-diphenylmethane bismaleimide resin. - Any one or a combination of at least two of diphenylisopropyl bismaleimide resin and 4,4'-diphenylsulfone bismaleimide resin;
优选地， 所述二烯丙基化合物选自二烯丙基双酚 A、 二烯丙基双酚 S、烯丙
基酚氧树脂、 烯丙基酚醛树脂、 二烯丙基二苯醚中的任意 1种或至少 2种的组 合。 Preferably, the diallyl compound is selected from diallyl bisphenol A, diallyl bisphenol S, allyl Any one or a combination of at least two of phenoloxy resin, allyl phenolic resin, and diallyl diphenyl ether.
5、 如权利要求 1〜4之一所述的组合物， 其特征在于， 所述固化剂选自双氰 胺、 芳香胺、 酸酐、 酚类固化剂、 异氰尿酸三烯酯或线性酚醛中的任意 1 种或 至少 2种的组合； 5. The composition according to one of claims 1 to 4, characterized in that the curing agent is selected from dicyandiamide, aromatic amines, acid anhydrides, phenolic curing agents, trienyl isocyanurates or novolacs Any 1 type or a combination of at least 2 types;
优选地， 所述填料选自氢氧化铝、 二氧化硅、 氢氧化镁、 高岭土、 水滑石 中的任意 1种或至少 2种的组合。 Preferably, the filler is selected from any one or a combination of at least two of aluminum hydroxide, silica, magnesium hydroxide, kaolin, and hydrotalcite.
6、 如权利要求 1〜5之一所述的组合物， 其特征在于， 所述溶剂选自酮类溶 剂、 烃类溶剂、 醇类溶剂、 醚类溶剂、 酯类溶剂或非质子溶剂中的任意 1 种或 至少 2种的组合； 所述酮类溶剂优选自丙酮、 甲基乙基酮或甲基异丁基酮中的 任意 1种或至少 2种的组合； 所述烃类溶剂优选甲苯和 /或二甲苯； 所述醇类溶 剂优选自甲醇、 乙醇、 或正丙醇中的任意 1种或至少 2种的组合； 所述醚类溶 剂优选乙二醇单甲醚和 /或丙二醇单甲醚； 所述酯类溶剂优选丙二醇甲醚醋酸酯 和 /或乙酸乙酯； 所述非质子溶剂优选 Ν,Ν-二甲基甲酰胺和 /或 Ν,Ν-二乙基甲酰 胺。 6. The composition according to one of claims 1 to 5, wherein the solvent is selected from ketone solvents, hydrocarbon solvents, alcohol solvents, ether solvents, ester solvents or aprotic solvents. Any one or a combination of at least two; the ketone solvent is preferably any one or a combination of at least two of acetone, methyl ethyl ketone or methyl isobutyl ketone; the hydrocarbon solvent is preferably toluene and/or xylene; the alcohol solvent is preferably any one or a combination of at least two of methanol, ethanol, or n-propanol; the ether solvent is preferably ethylene glycol monomethyl ether and/or propylene glycol mono Methyl ether; The ester solvent is preferably propylene glycol methyl ether acetate and/or ethyl acetate; the aprotic solvent is preferably N, N-dimethylformamide and/or N, N-diethylformamide.
7、 如权利要求 1〜6 之一所述的组合物， 其特征在于， 所述组成物还包括 0.01-1.0重量份的固化促进剂； 7. The composition according to one of claims 1 to 6, characterized in that the composition further includes 0.01-1.0 parts by weight of a curing accelerator;
优选地， 所述固化促进剂选自三级胺、 三级磷、 季胺盐、 季磷盐或咪唑化 合物中的任意 1种或至少 2种的组合。 Preferably, the curing accelerator is selected from any one or a combination of at least two of tertiary amines, tertiary phosphorus, quaternary ammonium salts, quaternary phosphorus salts or imidazole compounds.
8、 如权利要求 1〜7之一所述的组合物， 其特征在于， 所述树脂组合物由组 成物和溶剂组成； 所述组成物按重量份数包括如下组分： 8. The composition according to one of claims 1 to 7, characterized in that the resin composition consists of a composition and a solvent; the composition includes the following components in parts by weight:
无卤环氧树脂： 20〜100份； Halogen-free epoxy resin: 20~100 parts;
腈基树脂： 10〜30份；
烯丙基改性双马树脂： 20〜100份； Nitrile-based resin: 10~30 parts; Allyl modified bima resin: 20~100 parts;
固化剂： 20〜100份； Curing agent: 20~100 parts;
填料： 10〜100份； Filling: 10~100 parts;
固化促进剂： 0.01〜1.0份; Curing accelerator: 0.01~1.0 parts;
其中， 组成物溶于溶剂， 并且其占总重的重量百分比为 65%〜75%之间。 Wherein, the composition is dissolved in the solvent, and its weight percentage to the total weight is between 65% and 75%.
9、 一种半固化片， 由增强材料及浸润于增强材料上的基体材料组成， 其特 征在于， 所述基体材料为权利要求 1〜8之一所述的热固性树脂组合物。 9. A prepreg, consisting of a reinforcing material and a matrix material infiltrated on the reinforcing material, characterized in that the matrix material is the thermosetting resin composition according to one of claims 1 to 8.
10一种印制电路用覆金属箔层压板， 包括层压板及压覆于层压板的一侧或 两侧的金属箔， 所述层压板包括数片相贴合的半固化片， 其特征在于， 所述半 固化片由增强材料及浸润于增强材料上的基体材料组成， 所述基体材料为权利 要求 1〜8之一所述的热固性树脂组合物； 10. A metal foil-clad laminate for printed circuits, including a laminate and a metal foil pressed on one or both sides of the laminate. The laminate includes several prepregs that are laminated together, and is characterized in that: The prepreg is composed of a reinforcing material and a matrix material infiltrated on the reinforcing material, and the matrix material is the thermosetting resin composition according to one of claims 1 to 8;
优选地， 所述金属箔为铜箔。
Preferably, the metal foil is copper foil.
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| CN102850766A (en) * | 2012-09-20 | 2013-01-02 | 苏州生益科技有限公司 | Halogen-free resin composition, prepreg and laminated board made from the same |
| CN102976972A (en) * | 2012-12-03 | 2013-03-20 | 电子科技大学 | Nitrile resin monomer, nitrile resin polymer and preparation method of nitrile resin monomer and nitrile resin polymer |
| CN103265791A (en) * | 2013-05-29 | 2013-08-28 | 苏州生益科技有限公司 | Thermosetting resin composition for integrated circuit as well as prepreg and laminated board both fabricated by using composition |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020148667A1 (en) | 2018-11-12 | 2020-07-23 | Obs Technology As | Accumulator |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103897346A (en) | 2014-07-02 |
| CN103897346B (en) | 2017-07-11 |
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