低温快速固化环氧导电胶的制备与性能

285102011ActaMateriaeCompositaeSinicaVol28No5October2011:1000-3851(2011)05-0034-07:2010-09-27;:2011-04-01;:2011-05-1310:07:00::CNKI:11-1801/TB.20110513.1007.001:(50977001,51073015):,,,:E-mail:[e-mail]张博1,党智敏*1,2(1.,100029;2.,100083):E-51,(PA),(KH550)(),,,604h65%,3.610-4cm;17.6MPa85(RH)85%1000h10%:;;;;:TB332:APreparationandperformanceofepoxyresinconductiveadhesivewithfast-curingfeatureatlowtemperatureZHANGBo1,DANGZhimin*1,2(1.StateKeyLabofChemicalResourcesEngineering,BeijingUniversityofChemicalTechnology,Beijing100029,China;2.DepartmentofPolymerScienceandEngineering,SchoolofChemistryandBiologicalEngineering,UniversityofScience&TechnologyBeijing,Beijing100083,China)Abstract:Athermosettypeisotropicconductiveadhesive(ICA)waspreparedbyepoxyresinE-51asthematrix,nanosizedandmicrosizedcopperpowdermodifiedbysilanecouplingKH550astheconductivefillers,polyamideresinwithlowmolecularweightasthecuringagent,andsomeotheradditives.Anewliquidcuringagent,polyamideresinwithlowmolecularweight,wasusedwhichsolvedsomedifficultproblemsduringthepreparationofICA,suchaslimitofquantityofconductivefillers.Theeffectsofdifferentfactorssuchascuringagent,silanecouplingagent,reducer,andconductivefilleronthebondingperformanceandtheconductivityforconductiveadhesivewerediscussedbytheorthogonalexperiments.Thepreparationparametersoftheconductiveadhesivewereoptimized,andtheoptimalpreparationparametersfortheconductiveadhesivewasobtained.Theresultsshowthatoptimumconditionsofconductiveadhesivearecomposedof65%ofnano-andmicro-copperpowderwithcuringtimefor4hoursat60.Theadhesionstrengthreaches17.6MPaandthebulkresistivityis3.610-4cm.Thechangeratesofbulkresistivityarelessthan10%atthehightemperature(85)andthehighhumidity(RH85%).Keywords:conductiveadhesive;high-temperatureresistance;fastcuring;copperpowder;lowvolumeresistivity,Sn/Pb[1-3]:(1)Sn/Pb,0.65mm;(2)Pb,;(3)Sn/Pb,[4-5],,,,Sn/Pb[6],[7-8],,,,,,[9-14],(KH550),;,;E-51(PA),,,,;604h,Cu,PA,,11.1E-51(),;PA,;(,),;(KH550),;,1.2Cu/E-511.2.1环氧树脂(E-51)的预处理E-51(SF-02GB,),1201h,E-511.2.2铜粉的改性,1%,2%,3%KH550,,(JY92-11DN,),30min,(DZF-01,)1.2.3制备导电胶的工艺方法E-51,(SG65,)30min,,PA,,604h1.3Cu/E-51,(SX1934,SZ-82,);GB7124-86;FT-IR;SEM;TGA;(4294A,Agilent);(HTS-800,)22.11KH550KH550FTIR,KH550,FTIR1100~800cm-1SiOSi[15-16]KH550[17-19],,(EP),35,:1KH550FTIRFig.1FTIRspectraofcopperpowderbeforeandafterbeingmodifiedbysilanecouplingKH5502E-51FTIR,915.33cm-1,,:m(E-51)m(PA)=10050,,2E-51FTIRFig.2FTIRspectraofepoxyE-51adhesivesbeforeandaftercuring,1L9(34),2,34334,,:ABCD;,:ABDC,A2B2C2D3,1Cu/E-51Table1FactorsandlevelsoforthogonalexperimentofCu/E-51conductiveadhesivepreparationLevelFactorsMassfractionofcopperpowder(A)/%Massratioofmicro-andnano-particles(B)MassfractionofKH550(C)/%Massfractionofreductant(D)/%1603715265552637073372Cu/E-51L9(34)Table2AnalysistableofL9(3)4orthogonalexperimentalresultofCu/E-51conductiveadhesivepreparationNo.ABCDVolumeresistivity/(10-4cm)Adhesionstrength/MPa111115.118.9212224.218.0313334.517.6421233.917.3522313.716.7623124.116.3731323.216.0832133.015.8933213.115.6363Cu/E-51Table3VarianceanalysistableofvolumeresistivityofCu/E-51conductiveadhesiveFactorsSquareddeviationsDegreesoffreedomFratioFthresholdSignificantA3.38023.4663.110B0.28720.2943.110C0.18720.1923.110D0.04720.0483.110Error3.9084Cu/E-51Table4VarianceanalysistableofadhesionstrengthofCu/E-51conductiveadhesiveFactorsSquareddeviationsDegreesoffreedomFratioFthresholdSignificantA8.49623.4093.110B1.24220.4983.110C0.09620.0393.110D0.13620.0553.110Error9.9783Cu/E-51Fig.3EffectcurvesofvolumeresistivityandadhesionstrengthofCu/E-51conductiveadhesive65%552%7%2.2Cu/E-51465%Cu/E-51SEME-51,,[20]2.35,,,50%,,60%,,,,60%[21],,,2.46,-20~100,20%[9],,,,7Cu/E-51TGA,Cu/E-51:95.91~209.70,0.79%,100,;37,:465%Cu/E-51SEMFig.4SEMimagesoftheflat((a)~(d))andfracture((e),(f))surfacesofCu/E-51conductiveadhesivewith65%massfractionofCupowder20970~398.81,2.91%,Cu/E-512.55Cu/E-5185(RH)85%1000h10%5Cu/E-51Table5ParametertableofCu/E-51conductiveadhesivebeforeandafteragingVolumeresistivity/(10-4cm)Adhesionstrength/MPaBeforeaging3.617.6Afteraging3.916.1385Cu/E-51Fig.5RelationshipbetweenthevolumeresistivityandthecontentofcopperpowderinCu/E-51conductiveadhesive6Cu/E-51Fig.6CurvesofvolumeresistanceofCu/E-51conductiveadhesivewiththechangeoffrequencyandtemperature3(1)E-51,(PA)7Cu/E-51TGAFig.7TGAspectraofCu/E-51conductiveadhesive,,(KH550)(2),65%,7%(3)3.610-4cm,17.6MPa,:[1]SeppealeaA,RistolainenE.StudyofadhesiveflipchipbondingprocessandfailuremechanismsofACAjoints[J].MicroelectronicsReliability,2004,44(4):639-648.[2]ChinM,IyerKA,HuSJ.Predictionofelectricalcontactresistanceforanisotropicconductiveadhesiveassemblies[J].IEEETransactionsonComponentsandPackagingTechnologies,2004,27(2):317-326.[3]LuD,WongCP.Isotropicconductiveadhesivesfilledwithlow-melting-pointalloyfiller[J].IEEETransactionsonElectronicsPackagingManufacturing,2000,23(1):185-190.[4],,,,.[J].,2006,23(5):24-28.WuHaiping,WuXijun,LiuJinfang,WangYouwen,ZhangGuoqing.Isotropicalcondu