WO2017080040A1 - 一种耐湿热高可靠性环氧导电银胶及其制备方法与应用 - Google Patents

一种耐湿热高可靠性环氧导电银胶及其制备方法与应用 Download PDF

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Publication number
WO2017080040A1
WO2017080040A1 PCT/CN2015/098837 CN2015098837W WO2017080040A1 WO 2017080040 A1 WO2017080040 A1 WO 2017080040A1 CN 2015098837 W CN2015098837 W CN 2015098837W WO 2017080040 A1 WO2017080040 A1 WO 2017080040A1
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Prior art keywords
curing agent
silver paste
conductive silver
epoxy resin
epoxy
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PCT/CN2015/098837
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English (en)
French (fr)
Inventor
孙蓉
张保坦
韩延康
朱朋莉
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Shenzhen Institute of Advanced Technology of CAS
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Shenzhen Institute of Advanced Technology of CAS
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
    • C09J9/02—Electrically-conducting adhesives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins

Definitions

  • the invention relates to a moisture-resistant and high-reliability epoxy conductive silver glue, a preparation method and application thereof, and belongs to the technical field of microelectronic packaging.
  • conductive adhesives as a material that can replace lead-tin solder, have become the core material of the microelectronics industry. The importance is increasingly prominent. Because the conductive adhesive bonds the conductive particles together by the bonding of the matrix resin to form a conductive path, the conductive connection of the material to be bonded is realized.
  • the material has low bonding temperature, wide bonding temperature range, simple process, flexible and variable formulation, can be made into slurry, realizes fine pitch and ultra-fine pitch interconnection ability, and has good adhesion and is suitable for each Bonding of the surface of a type substrate (flexible substrate, ceramic/glass substrate, laminate, molding compound, etc.).
  • conductive adhesives also have some shortcomings in performance, such as high volume resistivity, poor thermal conductivity, insufficient bonding strength, unstable contact resistance, etc., especially after high temperature and high humidity aging experiments. It is easy to produce interface delamination, which leads to failure of bonding, electrical connection and mechanical properties. These have become important constraints limiting the application of conductive adhesives in the field of microelectronic assembly. Therefore, the development of conductive adhesive with high reliability has become the focus of current research.
  • epoxy resin is widely used in the electronics industry as coating coating material, bonding potting material and laminated composite material because of its excellent bonding property, mechanical strength and dimensional stability. Wait.
  • performance may be degraded, especially in an environment where the temperature is 50-60 ° C and the humidity exceeds 95%. The ability will continue to weaken, and may even directly fail, so that the epoxy resin material loses its original role, which poses a great challenge to the use of epoxy resin materials. Therefore, solving the moisture and heat resistance of materials has become a key issue in the research field of microelectronic package reliability.
  • the method for improving the heat and humidity resistance of an epoxy resin mainly improves the crosslinking density, introduces moist heat resistance and moisture resistance groups or segments, or reduces and blocks the polar groups generated in the cured structure. content.
  • Chinese patent CN 102329587A introduces a thermosetting phenolic resin to improve the structural compactness and heat resistance of the cured product, making the material less susceptible to electrochemical corrosion and reducing hygroscopicity.
  • the prepared conductive paste is at 85 ° C and 85% RH. After 500 hours of aging, the volume resistivity changes by less than 20%, remains on the order of 10 -5 ⁇ /cm, has good electrical conductivity and high contact resistance stability.
  • Chinese patent CN103409093A uses tetrafunctional N, N, N', N'-tetraglycidyl-4,4'-diaminodiphenyl ether epoxy resin as the main resin, which has a phenyl group in its molecular structure.
  • the high epoxy functionality gives the cured product a relatively high crosslink density and exhibits good high temperature resistance.
  • the resin has an ether bond in its molecular structure, and the molecular flexibility is good, which can improve the toughness and water resistance of the material.
  • the adhesive prepared by the method has a very low saturated moisture absorption rate of only 0.43%, and also has an ultra-high bonding strength of 36.9 MPa, and can be applied to glass, ceramic, metal, epoxy resin-based composite materials. Bonding of the substrate.
  • the molecular structure contains a tertiary amine, it can catalyze the epoxy polymerization itself, resulting in poor storage stability of the system, which in turn affects its special application in the electronics industry.
  • Chinese patent CN 102925100A is modified with hydrophobic phenyl silicone resin to give the material good temperature resistance. The maximum temperature can reach 300 ° C, the resistivity can reach 2-4 ⁇ 10 -5 ⁇ /cm, and the thermal conductivity is 4- 6w/k ⁇ m.
  • Chinese patent CN 101126003A introduces a macromolecular anthracene ring skeleton in the crosslinked network to improve the moisture and heat resistance of the material.
  • the water absorption rate of the material is reduced by 60%, about 1.4%, and It maintains a shear strength of 10 MPa or more at a high temperature of 200 ° C, and is particularly suitable for occasions where high shear strength is required in a hot and humid environment.
  • ruthenium-based epoxy resins are not currently commercially available, special custom synthesis is required, and the process is cumbersome, resulting in relatively expensive products.
  • Chinese patent CN 102786901A is composed by introducing a large proportion of polyamide imine segment in epoxy resin, because the main chain and side chain of the cured product contain a large amount of benzene ring and imide group, so that the molecular chain has Very large rigidity, tensile strength up to 160MPa, thermal decomposition temperature is also significantly improved, super high 400 °C.
  • the introduction of the polyamide imine molecular structure also uses partial fluorine substitution, which can exhibit good hydrophobicity and moist heat resistance.
  • conductive silver adhesives have some shortcomings in practical application, such as poor storage stability, high curing temperature, complicated synthesis process, etc., especially in semiconductor packaging enterprises, which are found for chip keys in practical applications.
  • the conductive silver paste used in the pre-aging process will have 6-10% red zone, which is the phenomenon of peeling and cracking of the chip and the bracket at the edge, which is due to the poor heat and humidity resistance of the bonding material used. Caused.
  • an object of the present invention is to provide a moisture-resistant and highly reliable epoxy conductive silver paste.
  • Another object of the present invention is to provide a method for preparing the above-mentioned moisture-resistant high-reliability epoxy conductive silver paste.
  • the present invention provides a moisture-resistant and high-reliability epoxy conductive silver paste, which is 100% by weight based on the total weight of the moisture-resistant and high-reliability epoxy conductive silver paste.
  • the oxygen conductive silver paste is prepared from the following raw materials: 65-85 wt% of metallic silver powder, 5.0-30 wt% of epoxy resin, 1-15 wt% of active heterocyclic compound having a triazine structure, and 0.5-10 wt% of acrylic acid. Resin, 1.0-3.5 wt% curing agent, 0.05-1.5 wt% accelerator and 0.01-3 wt% functional auxiliary.
  • the moisture-resistant heat-reliable epoxy conductive silver paste is prepared from the following raw materials, based on 100% of the total weight of the moisture-resistant heat-reliable epoxy conductive silver paste; 65-85 wt% metal silver powder, 5.0-30 wt% epoxy resin, 1-15 wt% active heterocyclic compound having a triazine structure, 0.5-10 wt% acrylic resin, 1.0-3.5 wt% curing agent 0.05-1.5 wt% of a promoter, 0.01-3 wt% of a functional auxiliary, and 1-10 wt% of a toughening diluent.
  • the metal silver powder is selected from one or a combination of spherical, flake, rod and dendritic metal silver powder;
  • the metal silver powder is a combination of a sheet metal silver powder and a spherical metal silver powder
  • the metal silver powder has a size of from 0.1 to 10 ⁇ m, further preferably from 0.5 to 5 ⁇ m.
  • the "size" of irregularly shaped metallic silver powder is defined in the art as the length of the longest portion of the plane.
  • the "combination of several metal silver powders" involved in the present invention may be a combination of several metal silver powders in any suitable ratio, and the present invention does not require a ratio relationship between the amounts of the metal silver powders, and those skilled in the art may According to the needs of on-site operation, the appropriate dosage ratio relationship is selected. However, it should be noted that the sum of the above-mentioned several kinds of conductive silver powders needs to meet the limit of the amount of raw materials used in the present invention.
  • the epoxy resin used in the present invention may be any epoxy resin which is suitable for the conductive silver paste disclosed in the prior art; preferably, the epoxy resin is selected from the group consisting of bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol F type epoxy resin, hydantoin epoxy resin, 4,4' diaminodiphenylmethane tetraglycidylamine type epoxy resin, triglycidyl P-aminophenol type epoxy resin, 4,5-epoxycyclohexane-1,2- a combination of one or more of diglycidyl dicarboxylate (TDE-85) epoxy resin, alicyclic epoxy resin, and novolac epoxy resin;
  • TDE-85 diglycidyl dicarboxylate
  • the epoxy resin is a low viscosity bisphenol F type epoxy resin, 4,5-epoxycyclohexane-1,2-dicarboxylic acid diglycidyl ester (TDE-85) epoxy resin, 4, 4' diaminodiphenylmethane tetraglycidylamine type epoxy resin and triglycidyl p-aminophenol type epoxy resin.
  • the "combination of several kinds of epoxy resins” involved in the present invention may be a combination of several kinds of epoxy resins in any suitable ratio, and the present invention does not require the proportional relationship between the amounts of the epoxy resins.
  • the technician can select the appropriate dosage ratio according to the needs of the field operation.
  • the sum of the above-mentioned several kinds of epoxy resins needs to meet the limitation of the amount of the raw materials of the present invention.
  • the alicyclic epoxy resin used is a conventional product in the art, and any of the alicyclic epoxy resins disclosed in the prior art which can be suitable for the conductive silver paste can be used.
  • the present invention preferably the alicyclic epoxy resin comprises 3,4-epoxycyclohexenemethyl-3,4-epoxycyclohexenoate, 4,5-epoxycyclohexane-1,2 - Diglycidyl dicarboxylate or bis((3,4-epoxycyclohexyl)methyl) adipate.
  • the hyacinol used is a conventional product in the art, and any of the hyacinol resins disclosed in the prior art which can be suitable for the conductive silver paste can be used in the present invention. .
  • the phenolic epoxy resin used is a conventional product in the art, and any of the phenolic epoxy resins disclosed in the prior art which can be suitable for the conductive silver paste can be used in the present invention;
  • the phenolic epoxy resin comprises a phenolic epoxy resin of the type EPALLOY-8240 produced by Emerald Corporation of the United States; a phenolic epoxy resin of the type NPPN-631 produced by Taiwan Nanya Plastic Industry Co., Ltd.
  • the phenolic epoxy resin produced by Dow Chemical (DOW) is DEN431 and DEN438; the phenolic epoxy resin produced by Guangzhou Kailuo Chemical Co., Ltd. is F-51.
  • the active heterocyclic compound having a triazine structure may be all compounds containing a triazine structure, and preferably, the active heterocyclic compound having a triazine structure is selected from 1, 2, 4-triazine, 1,3,5-triazine, 4-amino-1,3,5-triazin-2-one, 3-amino-5-phenyl-1,3,5-triazine, 2 , 4-diamino-6-phenyl-1,3,5-triazine, hexamethylene diisocyanate (HDI) trimer and its closure, toluene diisocyanate (TDI) trimer and its closure a combination of one or more of triglycidyl isocyanurate, triallyl isocyanurate, and amino-substituted benzotriazine derivatives;
  • HDI hexamethylene diisocyanate
  • TDI toluene diisocyanate
  • the active heterocyclic compound having a triazine structure includes triglycidyl isocyanurate or triallyl isocyanurate.
  • the "combination of several active heterocyclic compounds having a triazine structure" referred to in the present invention may be a combination of several active heterocyclic compounds having a triazine structure in any suitable ratio, and the present invention has three
  • the proportion relationship between the active heterocyclic compounds of the azine structure is not required, and those skilled in the art can select an appropriate dosage ratio according to the needs of the field operation, but it should be noted that the above several active impurities having a triazine structure
  • the sum of the amounts of the cyclic compounds needs to satisfy the limit of the amount of the raw materials used in the present invention.
  • the hexamethylene diisocyanate (HDI) trimer block and the toluene diisocyanate (TDI) trimer block are all conventional products in the art;
  • the diisocyanate (HDI) trimer block comprises a hexamethylene diisocyanate (HDI) trimer and a seal formed from phenol, caprolactam and butanone oxime, and the toluene diisocyanate (TDI) trimer block comprises A closure formed of a toluene diisocyanate (TDI) trimer with phenol, caprolactam, butanone oxime or the like.
  • amino-substituted benzotriazine derivatives used in accordance with the present invention are conventional products in the art, and in a preferred embodiment of the invention, 3-amino-7-methyl-1,2 , 4-benzotriazine-1-oxide or 3-biamino-7-methoxy-1,2,4-benzotriazine, and the like.
  • the acrylic resin used may be any epoxy resin which is suitable for the conductive silver paste disclosed in the prior art; preferably, the acrylic resin is selected from the group consisting of acrylate prepolymers, A combination of one or more of a polyfunctional acrylic resin, an epoxy modified acrylic resin, a polyurethane modified acrylic resin, a silicone modified acrylic resin, and a hyperbranched polyester modified acrylic resin.
  • the acrylate prepolymer used is a conventional product in the art, and a commercially available acrylate prepolymer can be used in the present invention.
  • the acrylic acid The ester prepolymer has a functionality of ⁇ 2 and a viscosity of ⁇ 10000 mPas.
  • the functional group participating in the reaction referred to in the definition of the functionality is an acrylate group.
  • the polyfunctional acrylic resin used is a conventional product in the art, and a commercially available polyfunctional acrylic resin can be used in the present invention.
  • the polyfunctional acrylic acid is used.
  • the resin includes an acrylic resin having a number of acrylate groups of ⁇ 2 and a viscosity of ⁇ 10 Pas.
  • the epoxy-modified acrylic resin, the polyurethane-modified acrylic resin, the silicone-modified acrylic resin, and the hyperbranched polyester-modified acrylic resin are all conventional products in the art, and any commercially available ones are commercially available.
  • the above substances can be used in the present invention.
  • the curing agent used may be any one of the curing agents disclosed in the prior art which can be suitable for the conductive silver paste; preferably, the curing agent is selected from the group consisting of an imidazole curing agent and an imidazole modification.
  • Sex agent curing agent One of an aromatic amine curing agent, a dicyandiamide, a dicyandiamide derivative curing agent, an organic acid hydrazide curing agent, a boron trifluoride-amine complex curing agent, and a microcapsule curing agent or Several combinations.
  • the "combination of several curing agents” involved in the present invention may be a combination of several curing agents in any suitable ratio, and the present invention does not require a ratio relationship between the curing agents, and those skilled in the art may According to the needs of on-site operation, the appropriate dosage ratio relationship is selected. However, it should be noted that the sum of the above-mentioned several curing agents needs to meet the limit of the amount of raw materials used in the present invention.
  • the imidazole curing agent used in the present invention is a conventional one in the art, and preferably the imidazole curing agent includes 2-methylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole or 1,2- Dimethylimidazole.
  • the imidazole modified material curing agent used in the present invention is a conventional material in the art, and preferably the imidazole modified material curing agent comprises a cyanoethyl modified imidazole curing agent, a long alkyl chain modified imidazole curing agent, PN-23, PN-31, PN-40 or PN-50;
  • the cyanoethyl modified imidazole curing agent comprises 1-cyanoethyl-2-ethyl-4-methylimidazole or 1-cyanoethyl-2-phenylimidazole;
  • the long alkyl chain-modified imidazole curing agent includes 2-heptadecylimidazole or 2,4-diamino-6-(2-undecylimidazolyl)-1-ethyltriazine.
  • the 2-heptadecylimidazole used is a C17Z long alkyl chain-modified imidazole curing agent manufactured by Shikoku Chemicals Co., Ltd.;
  • the 2,4-diamino-6-(2-undecyl imidazolyl)-1-ethyltriazine used is a long alkyl chain-modified imidazole of the type C11Z-A produced by Shikoku Chemicals Co., Ltd., Japan. Class curing agent;
  • the PN-23, PN-31, PN-40, and PN-50 used were all imidazole-modified curing agents produced by Ajinomoto Co., Ltd.
  • the aromatic amine curing agent used in the present invention is a conventional one in the art, and the aromatic amine curing agent includes 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfone, and Phenylenediamine, m-xylylenediamine or diethyltoluenediamine.
  • the dicyandiamide derivative curing agent used in the present invention is a conventional material in the art, and the dicyandiamide derivative curing agent includes a 3,5-disubstituted aniline modified dicyandiamide derivative and m-toluidine modified Sodium dicyandiamide or benzoquinone modified dicyandiamide; in a preferred embodiment of the invention, the 3,5-disubstituted aniline modified dicyandiamide derivative used is a model manufactured by Ciba-Geigy Co., Ltd. A dicyandiamide derivative curing agent for HT2833 and HT2844.
  • the organic acid hydrazide curing agent used in the present invention is a substance conventionally known in the art, and the organic acid hydrazide is cured.
  • the agent includes succinic acid hydrazide, adipic acid dihydrazide, sebacic acid hydrazide, isophthalic acid hydrazide or p-hydroxybenzoic acid hydrazide (POBH).
  • the boron trifluoride-amine complex type curing agent used in the present invention is a substance conventional in the art, and the boron trifluoride-amine complex type curing agent includes boron trifluoride and ethylamine, piperidine, and the like. a complex formed by ethylamine or aniline.
  • the microcapsule curing agent used in the present invention is a conventional curing agent used in the art.
  • the microcapsule curing agent used in the present invention includes Novacure HX3721, HX3721, and HX3921HP manufactured by Asahi Kasei Chemicals Co., Ltd., Japan. And HX3941HP poly polyamine modified imidazole microcapsule curing agent.
  • the accelerator used may be any one of the promoters disclosed in the prior art which is suitable for the conductive silver paste; preferably, the accelerator is selected from the group consisting of 2, 4, 6-three. (dimethylaminomethyl) phenol, tris(2-ethylhexanoic acid) salt of 2,4,6-tris(dimethylaminomethyl)phenol, imidazole compound and salt complex thereof, triphenylphosphine , tetrabutylphosphonium bromide, tetrabutylphosphonium acetate, tetrabutylphosphine oxide, benzyltriphenylphosphonium bromide, 1-cyanoethyl-2-ethyl-4-methylimidazole, tetramethylguanidine, A combination of one or more of a metal salt of benzoyl peroxide, organic urea, and acetylacetone.
  • the "combination of several accelerators” involved in the present invention may be a combination of several accelerators in any suitable ratio, and the present invention does not require a proportional relationship between the accelerators, and those skilled in the art may According to the needs of on-site operation, the appropriate dosage ratio relationship is selected. However, it should be noted that the sum of the above-mentioned several accelerators needs to meet the limit of the amount of raw materials used in the present invention.
  • the imidazole compound and the salt complex thereof used are products commonly used in the art, and in particular, the imidazole compound includes 2-ethyl-4-methylimidazole or 2-methyl group.
  • 4-Ethyl imidazole; a salt complex of an imidazole compound includes an imidazolium salt complex formed of the imidazole compound with copper sulfate, copper chloride, copper bromide, nickel chloride or the like.
  • the metal salt of acetylacetone used is a product commonly used in the art, and preferably the metal salt of acetylacetone includes an aluminum salt of acetylacetone, a cobalt salt of acetylacetone, a zinc salt of acetylacetone, a copper salt of acetylacetone, a nickel salt of acetylacetone, a manganese salt of acetylacetone, a chromium salt of acetylacetone, a titanium salt of acetylacetone or a zirconium salt of acetylacetone.
  • the metal salt of acetylacetone includes an aluminum salt of acetylacetone, a cobalt salt of acetylacetone, a zinc salt of acetylacetone, a copper salt of acetylacetone, a nickel salt of acetylacetone, a manganese salt of acetylacetone, a chromium salt of acetylacetone
  • the organic urea used includes N-p-chlorophenyl-N,N'-dimethylurea, dimethylimidazolium, and Evonik Degussa, respectively.
  • N-p-chlorophenyl-N,N'-dimethylurea dimethylimidazolium, and Evonik Degussa, respectively.
  • the models are OMICURE U-24M, OMICURE U-35M, OMICURE U-52M and OMICURE U-405M organic urea.
  • the toughening diluent used may be any toughening diluent which is suitable for the conductive silver paste disclosed in the prior art; preferably, the toughening diluent is selected from the end Carboxyl liquid nitrile rubber, hydroxyl terminated liquid nitrile rubber, terminal amino liquid nitrile rubber, terminal epoxy liquid nitrile rubber, terminal carboxyl liquid polybutadiene rubber, hydroxyl terminated liquid polybutadiene rubber, epoxy seal Polybutadiene rubber, liquid polyurethane, core-shell rubber particles, hyperbranched polyester, n-butyl glycidyl ether, 1,4-butanediol diglycidyl ether, trimethylolpropane glycidyl ether, C Alcohol triglycidyl ether, sterol glycidyl ether, ethylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether,
  • the "combination of several toughening diluents" referred to in the present invention may be a combination of several toughening diluents in any suitable ratio, and the present invention does not require a proportional relationship between the amounts of the toughening diluents.
  • Those skilled in the art can select an appropriate dosage ratio relationship according to the needs of the field operation.
  • the sum of the above-mentioned several kinds of toughening diluents needs to satisfy the limitation of the amount of raw materials in the present invention.
  • the core-shell rubber particles used are commercially available products in the field.
  • the core-shell rubber particles used may be produced by Wacker Chemie AG, Germany.
  • the hyperbranched polyester used is a conventional toughening diluent used in the art, and the toughening diluent may be any commercially available product, and in a preferred embodiment of the present invention,
  • the toughening thinner is selected from the hyperbranched polyester of HyPer H10, HyPer H20, HyPer H30 or HyPer H40 produced by Wuhan Hyperbranched Resin Technology Co., Ltd. and the Boltorn H20 and Boltorn H30 produced by Shanghai Xibao Biotechnology Co., Ltd. Hyperbranched polyester of Boltorn H40, Boltorn U3000, Boltorn W3000 or Boltorn H2004.
  • the functional auxiliary comprises one or a combination of an antifoaming agent, a dispersing agent, a leveling agent, a coupling agent and a thixotropic agent.
  • an antifoaming agent such as an antifoaming agent, a dispersing agent, a leveling agent, a coupling agent and a thixotropic agent to be added according to the requirements of the field operation.
  • the leveling agent is selected from the group consisting of TEGO900 and TEGO-B1484.
  • the antifoaming agent is selected from BYK-A530;
  • the thixotropic agent is selected from the group consisting of BYK-R605, fumed silica, hydrogenated castor oil or polyamide wax;
  • the dispersing agent is selected from the group consisting of BYK-110, NP-10, NP-15, NP-40, Span series (such as Span-80, etc.) or Tween series;
  • the coupling agent comprises ⁇ -aminopropyltriethoxysilane and ⁇ -aminopropyltrimethoxysilane (such as KH-550 produced by Nanjing Qianjin Chemical Co., Ltd.).
  • ⁇ -(2,3-epoxypropoxy)propyltrimethoxysilane such as KH-560 coupling agent produced by Nanjing Qianjin Chemical Co., Ltd.
  • ⁇ -(B Diamino)propyltrimethoxysilane 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane
  • isopropyl tris(10) Dialkylbenzenesulfonyl) titanate or distearyloxyisopropylaluminate such as KH-560 coupling agent produced by Nanjing Qianjin Chemical Co., Ltd.
  • the above TEGO900, TEGO-B1484, TEGO-410 and TEGO-245 are the corresponding auxiliary agents produced by German Digao; BYK-354, BYK-302, BYK-323, BYK-333, BYK -A530, BYK-R605, BYK-110 are the corresponding additives produced by BYK Chemicals in Germany; NP-10, NP-15 and NP-40 are the corresponding additives produced by Dow Chemical in the United States.
  • the invention also provides a preparation method of the above-mentioned moisture-resistant high-reliability epoxy conductive silver paste, which comprises the following steps:
  • the metal silver powder may be added in batches or may be added in one time, and those skilled in the art may select a suitable joining method to add metal silver powder according to the needs of field operations.
  • the above-described dispersion and grinding process can be carried out in a three-roll mill.
  • the order of adding the above various raw materials is not strictly required, but considering the stability of the above raw material products, in the preferred embodiment of the present invention, it is necessary to follow the above.
  • the feeding sequence defined in the preparation method is carried out in the order of addition.
  • the preparation process of the present invention is carried out at room temperature, and the present invention does not require time for each step, and those skilled in the art can control the appropriate time according to the requirements of the field operation, as long as the operation purpose can be achieved.
  • the invention also provides the above application of the moisture-resistant high-reliability epoxy conductive silver paste as a chip binder for electronic components and its application in electrode welding.
  • the electronic components include LEDs, carbon film potentiometers, chip resistors, tantalum/aluminum capacitors, NTC/PTC thermistors, quartz transistors, integrated circuits, and the like.
  • the active heterocyclic compound having a triazine structure containing an active reactive group and having heat and humidity resistance is introduced into the epoxy-based material, and an acrylic resin is added, and acrylic acid is added.
  • the resin can form a network interpenetrating dense structure with the epoxy resin during the curing process, thereby preparing the moisture-resistant high-reliability epoxy conductive silver paste of the present invention.
  • the moisture-resistant and high-reliability epoxy conductive silver adhesive of the invention not only has good electrical conductivity, but also has more excellent mechanical properties, bonding properties, especially moist heat resistance, so that the existing conductive silver rubber can be effectively solved. Poor heat and humidity and red zone problems in the aging process, and can also significantly improve the reliability of packaged devices and products; in addition, the conductive silver adhesive has a long pot life, good storage stability, low curing temperature, and development for the microelectronic packaging industry. Has a high practical value.
  • the viscosity of the moisture-resistant high-reliability epoxy conductive silver paste prepared by the present invention is 15000-20000 mPas, and the conductivity of the conductive silver paste after curing is 1-8 ⁇ 10 - 4 ⁇ /cm, shear strength 19-26MPa, maximum temperature up to 280°C.
  • the preparation method of the moisture-resistant and high-reliability epoxy conductive silver glue of the invention has the advantages of simple process and good controllability.
  • the embodiment provides a method for preparing a moisture-resistant high-reliability epoxy conductive silver paste, wherein the preparation method comprises the following steps:
  • the embodiment provides a method for preparing a moisture-resistant high-reliability epoxy conductive silver paste, wherein the preparation method comprises the following steps:
  • the bisphenol F type epoxy resin was weighed in order: 12 parts by weight, epoxy-terminated polybutadiene rubber: 2 parts by weight, triglycidyl isocyanurate: 5.0 parts by weight, epoxy-modified acrylate compound: 2.0 parts by weight, and uniformly mixed in a high-speed mixer to obtain a mixture A;
  • the embodiment provides a method for preparing a moisture-resistant high-reliability epoxy conductive silver paste, wherein the preparation method comprises the following steps:
  • the bisphenol A type epoxy resin was weighed in order: 12 parts by weight, epoxy-terminated polybutadiene rubber: 2 parts by weight, triallyl isocyanurate: 4.0 parts by weight, epoxy-modified acrylate Compound: 1.0 parts by weight, and mixed in a high-speed mixer to obtain a mixture A;
  • the embodiment provides a method for preparing a moisture-resistant high-reliability epoxy conductive silver paste, wherein the preparation method comprises the following steps:
  • the bisphenol A type epoxy resin was weighed in order: 12 parts by weight, epoxy-terminated polybutadiene rubber: 2 parts by weight, blocked type 1,6-hexamethylene diisocyanate trimer (hexamethylene diisocyanate (HDI) a blocking form of a trimer and phenol): 2.0 parts by weight, an epoxy-modified acrylate compound: 5.0 parts by weight, and uniformly mixed in a high-speed mixer to obtain a mixture A;
  • HDI hexamethylene diisocyanate
  • dicyandiamide was added to the obtained mixture A: 1.0 part by weight, 1-cyanoethyl-2-ethyl-4-methylimidazole: 0.7 part by weight, benzoyl peroxide: 0.5 part by weight, poly Amide wax: 0.3 parts by weight, KH-550 silane coupling agent: 0.3 parts by weight, TEGO-0.2 parts by weight, continue to mix and homogenize in a high-speed mixer to obtain a conductive silver gum matrix B;
  • the embodiment provides a method for preparing a moisture-resistant high-reliability epoxy conductive silver paste, wherein the preparation method comprises the following steps:
  • dicyandiamide was added to the obtained mixture A: 1.0 part by weight, 2-methyl-4-ethylimidazole: 0.7 part by weight, benzoyl peroxide: 0.5 part by weight, polyamide wax: 0.3 part by weight , KH-560 silane coupling agent: 0.3 parts by weight, TEGO-245: 0.2 parts by weight, and continue to mix it in a high-speed mixer to obtain a conductive silver paste matrix B;
  • the present comparative example provides a method for preparing a conductive silver paste, wherein the preparation method comprises the following steps:
  • the bisphenol F type epoxy resin was weighed in order: 15 parts by weight, epoxy-terminated polybutadiene rubber: 3 parts by weight, dicyandiamide: 1.6 parts by weight, organic urea (UR-500): 0.4 parts by weight, 1 , 4-butanediol diglycidyl ether: 2.0 parts by weight, polyamide wax: 0.3 parts by weight, KH-560 silane coupling agent: 0.3 parts by weight, TEGO-245: 0.2 parts by weight, and in a high-speed mixer Mixing it evenly to obtain a mixture A;
  • the conductive silver gum substrate prepared above is thoroughly stirred, placed in a three-roll mill for grinding, dispersing, and then filtered, vacuum defoamed, and packaged to obtain the conductive silver paste.
  • the present comparative example provides a method for preparing a conductive silver paste, wherein the preparation method comprises the following steps:
  • the bisphenol F type epoxy resin was weighed in order: 13 parts by weight, epoxy-terminated polybutadiene rubber: 2 parts by weight, liquid aromatic amine: 4.0 parts by weight, 2-methyl-4-ethylimidazole: 0.7 weight , 1,4-butanediol diglycidyl ether: 2.0 parts by weight, polyamide wax: 0.3 parts by weight, KH-560 silane coupling agent: 0.3 parts by weight, TEGO-245: 0.2 parts by weight, and at high speed Mixing it evenly in the mixer to obtain a mixture A;
  • the conductive silver gum substrate prepared above is thoroughly stirred, placed in a three-roll mill for grinding, dispersing, and then filtered, vacuum defoamed, and packaged to obtain the conductive silver paste.
  • the moisture-resistant high-reliability epoxy conductive silver paste prepared in Examples 1-5 and the prepared ratios of Comparative Examples 1 and 2 are prepared.
  • Conductive silver gel was tested and tested separately.
  • the test items mainly included viscosity, viscosity after storage for 24 hours, thixotropic index, glass transition temperature, bond strength, volume resistivity and thermal decomposition temperature.
  • the above viscosity and thixotropic index The glass transition temperature, bond strength, volume resistivity and thermal decomposition temperature are all measured by conventional techniques in the art. The relevant performance parameters are shown in Table 1.
  • High temperature aging test The standard reflow temperature commonly used in semiconductor packaging is 260 ° C, generally tested 3 times, each time about 15 seconds; in the examples of the present application, the high temperature aging experiment was carried out at 280 ° C, and the number of tests (5 times) More, each time duration (30s) is longer. It can be seen from Table 1 that the bonding strength of the conductive silver paste of the present application does not decrease significantly after experiencing more and more time of high temperature aging. High reliability.
  • Thermal shock test The experimental temperature is -40 ° C -150 ° C, and the number of thermal shocks is 200. From the experimental results in Table 1, it can be seen that the thermal shock has little effect on the bond strength of the system.
  • the conductive silver paste prepared in Examples 1-5 of the present invention has a volume resistivity of the order of l0 -4 ⁇ /cm after curing at 150 ° C / 90 min.
  • the thermal shock has little effect on the bond strength of the system, and the bond strength does not decrease significantly after high temperature and damp heat aging.
  • the bond strength of the conductive silver paste prepared by the individual examples is still certain.
  • the degree of improvement indicates that the conductive silver paste prepared by the invention has high reliability, and has excellent working characteristics, and is suitable for bonding and fixing of semiconductor chips.
  • the conductive silver paste prepared in Examples 1-5 of the present invention has a moderate viscosity, has substantially no change in viscosity after storage for 24 hours, and has a low viscosity at all times, which indicates that the conductive silver paste prepared by the present invention has good handleability.
  • the storage is stable and has a long pot life, which can meet the application requirements of current semiconductor packages.

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Abstract

本发明提供了一种耐湿热高可靠性环氧导电银胶及其制备方法与应用。以所述耐湿热高可靠性环氧导电银胶的总重量为100％计，该耐湿热高可靠性环氧导电银胶是由以下原料制备得到的：65-85％的金属银粉，5.0-30％的环氧树脂，1-15％的具有三嗪结构的活性杂环化合物，0.5-10％的丙烯酸树脂，1.0-3.5％的固化剂，0.05-1.5％的促进剂及0.01-3％的功能助剂。本发明还提供该导电银胶的制备方法及其应用。本发明所制备的导电银胶具有良好的导电性能、机械性能、粘结性能及耐湿热性能，可有效地改善现有导电银胶耐湿热性差以及老化过程出现红区的问题，同时还可以显著提高封装器件和产品的可靠性。

Description

一种耐湿热高可靠性环氧导电银胶及其制备方法与应用 技术领域
本发明涉及一种耐湿热高可靠性环氧导电银胶及其制备方法与应用，属于微电子封装技术领域。
背景技术
随着电子元件的小型化、微型化及印刷电路板的高密度化和高度集成化的迅速发展，导电胶作为一种可以取代铅锡焊料的材料，已经成为微电子工业的核心基础材料，其重要性日益突出。因为导电胶是通过基体树脂的粘接作用把导电粒子结合在一起，形成导电通路，实现被粘材料的导电连接。该类材料具有粘结温度低，粘结温度范围宽，工艺简单，配方灵活多变，可以制成浆料，实现细间距和超细间距的互连能力，且粘结性好，适应于各类型基板(柔性基板、陶瓷/玻璃基板、层压板及模塑料等)表面的粘结。同时，其还具有环境兼容性好、生产效率高、成本低等优点，使得其更能满足现代微电子工业对导电连接的需求。然而，与金属焊料相比，导电胶在性能上也存在一些不足，譬如体积电阻率偏高、导热性差、粘接强度不够、接触电阻不稳定等问题，尤其是经过高温高湿老化实验后，易产生界面分层，从而导致键合、电连接失效，机械性能下降，这些成为限制导电胶在微电子组装领域应用的重要制约因素。因此，开发具有高可靠性导电胶成为当前研究的重点。
环氧树脂作为导电胶的基础树脂，因其具有优良的粘结性能、机械强度以及尺寸稳定性，而被广泛用于电子工业做涂层披覆材料、粘结灌封材料、层压复合材料等。然而，在实践中发现，环氧树脂材料在湿热的环境中使用一段时间后，就可能会出现性能减弱的情况，特别是在温度为50-60℃，湿度超过95％的环境中，其承载能力会不断的减弱，甚至还可能直接失效，从而使得环氧树脂材料失去其原本的作用，这对环氧树脂材料的使用提出了极大挑战。因此，解决材料的耐湿热性能成为微电子封装可靠性研究领域的一个关键问题。
当前，提高环氧树脂的耐湿热性能的方法则主要是提高其交联密度、引入耐湿热性和耐湿性基团或链段，或是减少和封闭固化物结构中所产生的极性基团含量。譬如中国专利CN 102329587A引入热固型酚醛树脂，提高固化产物的结构致密性和耐热 性，使得材料不易发生电化学腐蚀并能降低吸湿性，所制备得到的导电胶在85℃和85％RH下老化500小时之后，其体积电阻率变化小于20％，仍保持在10-5Ω/cm量级，具有良好的导电性能和较高的接触电阻稳定性。但是该胶粘结强度只有8Mpa，导致可靠性还不够理想。中国专利CN103409093A则采用四官能N,N,N’,N’-四缩水甘油基-4,4’-二氨基二苯醚环氧树脂作为主体树脂，由于其分子结构中含有苯基，具有较高的环氧官能度，使得固化产物交联密度比较高，并表现出良好的耐高温特性。同时，该树脂分子结构中含有醚键，分子柔韧性较好，可以改善材料韧性和耐水性。通过该法制备得到的胶粘剂经固化后，其饱和吸湿率非常小，仅有0.43％，同时还具有36.9MPa的超高粘结强度，可应用于玻璃、陶瓷、金属、环氧树脂基复合材料等基材的粘接。然而，由于分子结构中含有叔胺，自身可以催化环氧聚合，导致该体系储存稳定性不太好，进而影响到其在电子行业的特殊应用。中国专利CN 102925100A采用疏水的苯基有机硅树脂改性，赋予材料良好的耐温性，最高使用温度可以达到300℃，电阻率达到2-4×10-5Ω/cm，导热率为4-6w/k·m。中国专利CN 101126003A则是在交联网络中引入大分子芴环骨架来提高材料的耐湿热性能，通过与常规改性环氧树脂相比，材料吸水率降低了60％，约为1.4％，且在200℃高温下仍保持10MPa以上的剪切强度，特别适合一些用在湿热环境下对高温剪切强度要求较高的场合。然而，由于含芴基的环氧树脂目前尚没有商业化的产品，因此需要专门订制合成，工艺比较繁琐，导致价格比较昂贵。中国专利CN 102786901A则是通过在环氧树脂中引入大比例的聚酰胺亚胺链段组成，因其固化物的主链和侧链中含有大量的苯环和亚酰胺基团，使得分子链具有很大的刚性，拉伸强度最高可达160MPa，热分解温度也显著提高，超高400℃。另外，引入聚酰胺亚胺分子结构中还采用部分氟取代，可以表现出很好的疏水性和耐湿热性能。尽管以上几种途径都很好地解决了环氧树脂材料的耐湿热性能，然而在实际应用中均存在不同程度的缺陷，譬如储存稳定性差、固化温度过高、合成工艺复杂，且该胶固化温度需要达到190℃，在此温度条件下，电子元器件容易损坏，因此只适于高温高压等特殊领域的应用。
目前，现有的导电银胶在实际应用过程中均存在一些不足之处，如储存稳定性差、固化温度过高、合成工艺复杂等，尤其是半导体封装企业在实际应用过程中发现用于芯片键合用的导电银胶在预老化过程中会出现6-10％的红区，即芯片与支架在边缘处发生剥离和开裂等现象，这是由于其所用的粘结材料耐湿热性能较差等原因造成的。
发明内容
为解决上述技术问题，本发明的目的在于提供一种耐湿热高可靠性环氧导电银胶。
本发明的目的还在于提供上述耐湿热高可靠性环氧导电银胶的制备方法。
本发明的目的还在于提供上述耐湿热高可靠性环氧导电银胶作为电子元器件的芯片粘结剂的应用及其在电极焊接中的应用。
为达到上述目的，本发明提供了一种耐湿热高可靠性环氧导电银胶，以所述耐湿热高可靠性环氧导电银胶的总重量为100％计，该耐湿热高可靠性环氧导电银胶是由以下原料制备得到的：65-85wt％的金属银粉，5.0-30wt％的环氧树脂，1-15wt％的具有三嗪结构的活性杂环化合物，0.5-10wt％的丙烯酸树脂，1.0-3.5wt％的固化剂，0.05-1.5wt％的促进剂及0.01-3wt％的功能助剂。
根据本发明所述的银胶，优选地，以所述耐湿热高可靠性环氧导电银胶的总重量为100％计，该耐湿热高可靠性环氧导电银胶是由以下原料制备得到的：65-85wt％的金属银粉，5.0-30wt％的环氧树脂，1-15wt％的具有三嗪结构的活性杂环化合物，0.5-10wt％的丙烯酸树脂，1.0-3.5wt％的固化剂，0.05-1.5wt％的促进剂、0.01-3wt％的功能助剂及1-10wt％的增韧稀释剂。
根据本发明所述的银胶，优选地，所述金属银粉选自球形、片状、棒状和树枝状金属银粉中的一种或几种的组合；
更优选所述金属银粉为片状金属银粉与球形金属银粉的组合；
还更优选所述金属银粉的尺寸为0.1-10μm，进一步优选为0.5-5μm。本领域将不规则形状金属银粉的“尺寸”定义为其平面上最长部分的长度。
本发明中涉及的“几种金属银粉的组合”可以为几种金属银粉按照任何合适的比例进行的组合，本发明对这几种金属银粉之间的用量比例关系不作要求，本领域技术人员可以根据现场作业需要，选择合适的用量比例关系，但是，需要注意的是，上述几种导电银粉的用量总和需要满足本发明对原料用量的限定。
根据本发明所述的银胶，本发明所用的环氧树脂可以为现有技术中公开的可适合于导电银胶的任何一种环氧树脂；优选地，所述环氧树脂选自双酚A型环氧树脂、氢化双酚A型环氧树脂、双酚F型环氧树脂、海因环氧树脂、4,4’二氨基二苯甲烷四缩水甘油胺型环氧树脂、三缩水甘油基对氨基苯酚型环氧树脂、4,5-环氧环己烷-1,2- 二甲酸二缩水甘油酯(TDE-85)环氧树脂、脂环族环氧树脂和酚醛环氧树脂中的一种或几种的组合；
更优选所述环氧树脂为低粘度的双酚F型环氧树脂、4,5-环氧环己烷-1,2-二甲酸二缩水甘油酯(TDE-85)环氧树脂、4,4’二氨基二苯甲烷四缩水甘油胺型环氧树脂及三缩水甘油基对氨基苯酚型环氧树脂等。
本发明中涉及的“几种环氧树脂的组合”可以为几种环氧树脂按照任何合适的比例进行的组合，本发明对这几种环氧树脂之间的用量比例关系不作要求，本领域技术人员可以根据现场作业需要，选择合适的用量比例关系，但是，需要注意的是，上述几种环氧树脂的用量总和需要满足本发明对原料用量的限定。
根据本发明所述的银胶，所用的脂环族环氧树脂为本领域的常规产品，现有技术中公开的可适合于导电银胶的任何一种脂环族环氧树脂均可以用于本发明；优选所述脂环族环氧树脂包括3,4-环氧环己烯甲基-3,4-环氧环己烯酸酯、4,5-环氧环己烷-1,2-二甲酸二缩水甘油酯或双((3,4-环氧环己基)甲基)己二酸酯。
根据本发明所述的银胶，所用的海因环氧树脂为本领域的常规产品，现有技术中公开的可适合于导电银胶的任何一种海因环氧树脂均可以用于本发明。
根据本发明所述的银胶，所用的酚醛环氧树脂为本领域的常规产品，现有技术中公开的可适合于导电银胶的任何一种酚醛环氧树脂均可以用于本发明；在本发明优选的实施方式中，所述酚醛环氧树脂包括美国Emerald公司生产的型号为EPALLOY-8240的酚醛环氧树脂；台湾南亚塑胶工业股份有限公司生产的型号为NPPN-631的酚醛环氧树脂；美国陶氏化学(DOW)生产的型号为DEN431、DEN438的酚醛环氧树脂；广州凯绿葳化工有限公司生产的型号为F-51的酚醛环氧树脂。
根据本发明所述的银胶，所述具有三嗪结构的活性杂环化合物可以为含有三嗪结构的所有化合物，优选地，所述具有三嗪结构的活性杂环化合物选自1,2,4-三嗪、1,3,5-三嗪、4-氨基-1,3,5-三嗪-2-酮、3-氨基-5-苯基-1,3,5-三嗪、2,4-二氨基-6-苯基-1,3,5-三嗪、六亚甲基二异氰酸酯(HDI)三聚体及其封闭物、甲苯二异氰酸酯(TDI)三聚体及其封闭物、异氰尿酸三缩水甘油酯、三烯丙基异氰脲酸酯和氨基取代苯并三嗪类衍生物中的一种或几种的组合；
更优选所述具有三嗪结构的活性杂环化合物包括异氰尿酸三缩水甘油酯或三烯丙基异氰脲酸酯。
本发明中涉及的“几种具有三嗪结构的活性杂环化合物的组合”可以为几种具有三嗪结构的活性杂环化合物按照任何合适的比例进行的组合，本发明对这几种具有三嗪结构的活性杂环化合物之间的用量比例关系不作要求，本领域技术人员可以根据现场作业需要，选择合适的用量比例关系，但是，需要注意的是，上述几种具有三嗪结构的活性杂环化合物的用量总和需要满足本发明对原料用量的限定。
根据本发明所述的银胶，所用的六亚甲基二异氰酸酯(HDI)三聚体封闭物及甲苯二异氰酸酯(TDI)三聚体封闭物均为本领域常规的产品；其中，六亚甲基二异氰酸酯(HDI)三聚体封闭物包括六亚甲基二异氰酸酯(HDI)三聚体与苯酚、己内酰胺及丁酮肟等形成的封闭物，甲苯二异氰酸酯(TDI)三聚体封闭物包括甲苯二异氰酸酯(TDI)三聚体与苯酚、己内酰胺及丁酮肟等形成的封闭物。
根据本发明所述的银胶，所用的氨基取代苯并三嗪类衍生物为本领域的常规产品，在本发明优选的实施方式中，其包括3-氨基-7-甲基-1,2,4-苯并三嗪-1-氧化物或3-联氨基-7-甲氧基-1,2,4-苯并三嗪等。
根据本发明所述的银胶，所用的丙烯酸树脂可以为现有技术中公开的可适合于导电银胶的任何一种环氧树脂；优选地，所述丙烯酸树脂选自丙烯酸酯预聚物、多官能团丙烯酸树脂、环氧改性丙烯酸树脂、聚氨酯改性丙烯酸树脂、有机硅改性丙烯酸树脂和超支化聚酯改性丙烯酸树脂中的一种或几种的组合。
根据本发明所述的银胶，所用的丙烯酸酯预聚物为本领域常规的产品，市售的丙烯酸酯预聚物均可以用于本发明，在本发明优选的实施方式中，所述丙烯酸酯预聚物的官能度≥2，粘度≤10000mPas。其中，官能度定义中所指的参加反应的官能团为丙烯酸酯基。
根据本发明所述的银胶，所用的多官能团丙烯酸树脂为本领域的常规产品，市售的多官能团丙烯酸树脂均可以用于本发明，在本发明优选的实施方式中，所述多官能团丙烯酸树脂包括丙烯酸酯基的数目≥2，粘度≤10Pas的丙烯酸树脂。
根据本发明所述的银胶，所用的环氧改性丙烯酸树脂、聚氨酯改性丙烯酸树脂、有机硅改性丙烯酸树脂、超支化聚酯改性丙烯酸树脂均为本领域的常规产品，任何市售的上述物质均可以用于本发明。
根据本发明所述的银胶，所用的固化剂可以为现有技术中公开的可适合于导电银胶的任何一种固化剂；优选地，所述固化剂选自咪唑类固化剂、咪唑改性物类固化剂、 芳香族胺类固化剂、双氰胺、双氰胺衍生物类固化剂、有机酸酰肼类固化剂、三氟化硼-胺络合物类固化剂及微胶囊固化剂中的一种或几种的组合。
本发明中涉及的“几种固化剂的组合”可以为几种固化剂按照任何合适的比例进行的组合，本发明对这几种固化剂之间的用量比例关系不作要求，本领域技术人员可以根据现场作业需要，选择合适的用量比例关系，但是，需要注意的是，上述几种固化剂的用量总和需要满足本发明对原料用量的限定。
本发明所用的咪唑类固化剂为本领域常规的物质，优选所述咪唑类固化剂包括2-甲基咪唑、2-苯基咪唑、2-乙基-4-甲基咪唑或1,2-二甲基咪唑。
本发明所用的咪唑改性物类固化剂为本领域常规的物质，优选所述咪唑改性物类固化剂包括氰乙基改性咪唑类固化剂、长烷基链改性咪唑类固化剂、PN-23、PN-31、PN-40或PN-50；
更优选所述氰乙基改性咪唑类固化剂包括1-氰乙基-2-乙基-4-甲基咪唑或1-氰乙基-2-苯基咪唑；
所述长烷基链改性咪唑类固化剂包括2-十七烷基咪唑或2,4-二氨基-6-(2-十一烷基咪唑基)-1-乙基三嗪。
在本发明优选的实施方式中，所用的2-十七烷基咪唑为日本四国化成工业株式会社生产的型号为C17Z的长烷基链改性咪唑类固化剂；
所用的2,4-二氨基-6-(2-十一烷基咪唑基)-1-乙基三嗪为日本四国化成工业株式会社生产的型号为C11Z-A的长烷基链改性咪唑类固化剂；
所用的PN-23、PN-31、PN-40及PN-50均为日本味之素株式会社生产的咪唑改性物类固化剂。
本发明所用的芳香族胺类固化剂为本领域常规的物质，所述芳香族胺类固化剂包括4,4’-二氨基二苯甲烷、4,4’-二氨基二苯基砜、间苯二胺、间苯二甲胺或二乙基甲苯二胺。
本发明所用的双氰胺衍生物类固化剂为本领域常规的物质，所述双氰胺衍生物类固化剂包括3,5-二取代苯胺改性的双氰胺衍生物、间甲苯胺改性的双氰胺或苯肼改性的双氰胺；在本发明优选的实施方式中，所用的3,5-二取代苯胺改性的双氰胺衍生物为Ciba-Geigy公司生产的型号为HT2833及HT2844的双氰胺衍生物类固化剂。
本发明所用的有机酸酰肼类固化剂为本领域常规的物质，所述有机酸酰肼类固化 剂包括琥珀酸酰肼、己二酸二酰肼、癸二酸酰肼、间苯二甲酸酰肼或对羟基安息香酸酰肼(POBH)。
本发明所用的三氟化硼-胺络合物类固化剂为本领域常规的物质，所述三氟化硼-胺络合物类固化剂包括三氟化硼与乙胺、哌啶、三乙胺或苯胺形成的络合物。
本发明所用的微胶囊固化剂为本领域使用的常规固化剂，在本发明优选的实施方式中，本发明所用的微胶囊固化剂包括日本旭化成化学株式会社生产的型号为Novacure HX3721、HX3721、HX3921HP及HX3941HP的聚多胺改性咪唑类微胶囊固化剂。
根据本发明所述的银胶，所用的促进剂可以为现有技术中公开的可适合于导电银胶的任何一种促进剂；优选地，所述促进剂选自2,4,6-三(二甲氨基甲基)苯酚、2,4,6-三(二甲氨基甲基)苯酚的三(2-乙基己酸)盐、咪唑类化合物及其盐络合物、三苯基膦、四丁基溴化膦、四丁基醋酸膦、四丁基氢氧化膦、苄基三苯基溴化膦、1-氰乙基-2-乙基-4-甲基咪唑、四甲基胍、过氧化苯甲酰、有机脲和乙酰丙酮的金属盐中的一种或几种的组合。
本发明中涉及的“几种促进剂的组合”可以为几种促进剂按照任何合适的比例进行的组合，本发明对这几种促进剂之间的用量比例关系不作要求，本领域技术人员可以根据现场作业需要，选择合适的用量比例关系，但是，需要注意的是，上述几种促进剂的用量总和需要满足本发明对原料用量的限定。
根据本发明所述的银胶，所用的咪唑类化合物及其盐络合物为本领域常用的产品，具体地所述咪唑类化合物包括2-乙基-4-甲基咪唑或2-甲基-4-乙基咪唑；咪唑类化合物的盐络合物包括所述咪唑类化合物与硫酸铜、氯化铜、溴化铜及氯化镍等形成的咪唑盐络合物。
根据本发明所述的银胶，所用的乙酰丙酮的金属盐为本领域常用的产品，优选所述乙酰丙酮的金属盐包括乙酰丙酮的铝盐、乙酰丙酮的钴盐、乙酰丙酮的锌盐、乙酰丙酮的铜盐、乙酰丙酮的镍盐、乙酰丙酮的锰盐、乙酰丙酮的铬盐、乙酰丙酮的钛盐或乙酰丙酮的锆盐。
根据本发明所述的银胶，所用的有机脲包括N-对氯苯基-N,N′-二甲基脲、二甲基咪唑脲、德国德固赛公司(Evonik Degussa)生产的型号分别为UR-200、UR-300及UR-500的有机脲、美国Emerald公司(Emerald Performance Materials LLC)生产的 型号分别为OMICURE U-24M、OMICURE U-35M、OMICURE U-52M及OMICURE U-405M的有机脲。
根据本发明所述的银胶，所用的增韧稀释剂可以为现有技术中公开的可适合于导电银胶的任何一种增韧稀释剂；优选地，所述增韧稀释剂选自端羧基液体丁腈橡胶、端羟基液体丁腈橡胶、端氨基液体丁腈橡胶、端环氧基液体丁腈橡胶、端羧基液体聚丁二烯橡胶、端羟基液体聚丁二烯橡胶、环氧封端的聚丁二烯橡胶、液体聚氨酯、核壳橡胶粒子、超支化聚酯、正丁基缩水甘油醚、l,4-丁二醇二缩水甘油醚、三羟甲基丙烷缩水甘油醚、丙三醇三缩水甘油醚、糠醇缩水甘油醚、乙二醇二缩水甘油醚、新戊二醇二缩水甘油醚、烯丙基缩水甘油醚、苯基缩水甘油醚、苄基缩水甘油醚、2-乙基己基缩水甘油醚、C12-C14烷基缩水甘油醚、二乙二醇缩水甘油醚、对叔丁基缩水甘油醚、环已二醇二缩水甘油醚和间苯二酚二缩水甘油醚中的一种或几种的组合。
本发明中涉及的“几种增韧稀释剂的组合”可以为几种增韧稀释剂按照任何合适的比例进行的组合，本发明对这几种增韧稀释剂之间的用量比例关系不作要求，本领域技术人员可以根据现场作业需要，选择合适的用量比例关系，但是，需要注意的是，上述几种增韧稀释剂的用量总和需要满足本发明对原料用量的限定。
根据本发明所述的银胶，所用的核壳橡胶粒子为本领域常用、市售的产品，在本发明优选的实施方式中，所用的核壳橡胶粒子可以是德国瓦克化学有限公司生产的型号为P52的核壳橡胶粒子。
根据本发明所述的银胶，所用的超支化聚酯为本领域使用的常规增韧稀释剂，该增韧稀释剂可以是任何市售的产品，在本发明优选的实施方式中，所用的增韧稀释剂选自武汉超支化树脂科技有限公司生产的型号为HyPer H10、HyPer H20、HyPer H30或HyPer H40的超支化聚酯及上海西宝生物科技有限公司生产的型号为Boltorn H20、Boltorn H30、Boltorn H40、Boltorn U3000、Boltorn W3000或Boltorn H2004的超支化聚酯。
根据本发明所述的银胶，优选地，所述功能助剂包括消泡剂、分散剂、流平剂、偶联剂和触变剂中的一种或几种的组合。本领域技术人员可以根据现场作业要求从消泡剂、分散剂、流平剂、偶联剂和触变剂等功能助剂中选择其中的一种或几种的组合进行添加。
在本发明优选的实施方式中，所述流平剂选自TEGO900、TEGO-B1484、 TEGO-410、TEGO-245、BYK-354、BYK-302、BYK-323或BYK-333；
在本发明优选的实施方式中，所述消泡剂选自BYK-A530；
在本发明优选的实施方式中，所述触变剂选自BYK-R605、气相二氧化硅、氢化蓖麻油或聚酰胺蜡；
在本发明优选的实施方式中，所述分散剂选自BYK-110、NP-10、NP-15、NP-40、Span系列(如Span-80等)或Tween系列；
在本发明优选的实施方式中，所述偶联剂包括γ-氨丙基三乙氧基硅烷、γ-氨丙基三甲氧基硅烷(如南京向前化工有限公司生产的型号为KH-550的偶联剂)、γ-(2,3-环氧丙氧基)丙基三甲氧基硅烷(如南京向前化工有限公司生产的型号为KH-560的偶联剂)、γ-(乙二胺基)丙基三甲氧基硅烷、2-(3,4-环氧环己基)乙基三甲氧基硅烷、异丙基三(异硬脂酰基)钛酸酯、异丙基三(十二烷基苯磺酰基)钛酸酯或二硬脂酰氧异丙基铝酸酯。
根据本发明所述的银胶，上述TEGO900、TEGO-B1484、TEGO-410及TEGO-245为德国迪高生产的相应助剂；BYK-354、BYK-302、BYK-323、BYK-333、BYK-A530、BYK-R605、BYK-110为德国毕克化学生产的相应助剂；NP-10、NP-15、NP-40为美国陶氏化学生产的相应助剂。
本发明还提供了上述耐湿热高可靠性环氧导电银胶的制备方法，该制备方法包括以下步骤：
a、将环氧树脂、增韧稀释剂、具有三嗪结构的活性杂环化合物及丙烯酸树脂混合均匀，得到混合物A；
b、向混合物A中依次加入固化剂、促进剂和功能助剂，得到胶体B；
c、将金属银粉加入到所述胶体B中，搅拌均匀，再经分散，研磨，过滤、真空脱泡、包装，得到所述耐湿热高可靠性环氧导电银胶。
根据本发明所述的制备方法，所述金属银粉可以分批次加入也可以一次性加入，本领域技术人员可以根据现场作业需要选择合适的加入方式加入金属银粉。
根据本发明所述的制备方法，在本发明优选的实施方式中，上述分散，研磨过程可以在三辊研磨机中进行。
根据本发明所述的制备方法，本发明对上述各种原料的加入顺序并没有严格的要求，但是，综合考虑上述原料产品的稳定性，在本发明优选的实施方式中需要按照上 述制备方法中限定的加料顺序进行加料。此外，本发明的制备过程是在室温下进行的，本发明对各步骤的时间不作要求，本领域技术人员可以根据现场作业要求控制合适的时间，只要能够实现操作的目的即可。
本发明还提供了上述耐湿热高可靠性环氧导电银胶作为电子元器件的芯片粘结剂的应用及其在电极焊接中的应用。
根据本发明所述的应用，所述电子元器件包括LED、碳膜电位器、片式电阻、钽/铝电容、NTC/PTC热敏电阻、石英晶体管、集成电路等。
本发明在制备耐湿热高可靠性环氧导电银胶时，在环氧基体材料中引入含有活性反应基团且耐湿热的具有三嗪结构的活性杂环化合物，并添加丙烯酸树脂，加入的丙烯酸树脂可以与环氧树脂在固化过程中形成网络互穿致密结构，进而制备得到本发明的耐湿热高可靠性环氧导电银胶。
本发明的耐湿热高可靠性环氧导电银胶不仅具有良好的导电性能，其还具备更加优异的机械性能、粘结性能，尤其是耐湿热性能，从而可以有效地解决现有导电银胶耐湿热性差以及老化过程出现红区的问题，同时还可以显著提高封装器件和产品的可靠性；此外，该导电银胶适用期长，储存稳定性好，固化温度低，对于微电子封装行业的发展具有很高的实用价值。在本发明优选的实施方式中，经检测，本发明制备得到的耐湿热高可靠性环氧导电银胶的粘度为15000-20000mPas，固化后该导电银胶的导电率为1-8×10-4Ω/cm，剪切强度为19-26MPa，最高使用温度可达280℃。
本发明耐湿热高可靠性环氧导电银胶的制备方法工艺简单，可控性好。
具体实施方式
为了对本发明的技术特征、目的及其有益效果有更加清楚地理解，现结合以下具体实施例对本发明的技术方案进行以下详细说明，但是不能将其理解为对本发明的可实施范围的具体限定。
实施例1
本实施例提供了一种耐湿热高可靠性环氧导电银胶的制备方法，其中，该制备方法包括以下步骤：
依次称取双酚F型环氧树脂：12重量份，超支化聚酯改性增韧剂：2重量份，三烯丙基异氰脲酸酯：4.0重量份，环氧改性丙烯酸酯类化合物：1重量份，三羟甲基丙烷缩水甘油醚：3.0重量份，并在高速混料机中将其混合均匀，得到混合物A；
然后向所述得到的混合物A中加入2-甲基-4-乙基咪唑：0.7重量份，双氰胺：1.0重量份，过氧化苯甲酰：0.5重量份，聚酰胺蜡：0.3重量份，KH-560硅烷偶联剂：0.3重量份，TEGO-245:0.2重量份，在高速混料机中继续将其混合均匀，得到导电银胶基体B；
最后分批将75重量份的银粉加入到上述制备得到的导电银胶基体B中并充分搅拌，再放入三辊研磨机进行研磨、分散，经过滤、真空脱泡、包装，即可得到耐湿热高可靠性环氧导电银胶。
实施例2
本实施例提供了一种耐湿热高可靠性环氧导电银胶的制备方法，其中，该制备方法包括以下步骤：
依次称取双酚F型环氧树脂：12重量份，环氧封端的聚丁二烯橡胶：2重量份，异氰尿酸三缩水甘油酯：5.0重量份，环氧改性丙烯酸酯类化合物：2.0重量份，并在高速混料机中将其混合均匀，得到混合物A；
然后向所述得到的混合物A中加入双氰胺：1.0重量份，2-甲基-4-乙基咪唑：0.7重量份，过氧化苯甲酰：0.5重量份，氢化蓖麻油：0.3重量份，KH-560硅烷偶联剂：0.3重量份，NP-10：0.2重量份，在高速混料机中继续将其混合均匀，得到导电银胶基体B；
最后分批将76重量份的银粉加入到上述制备得到的导电银胶基体B中并充分搅拌，再放入三辊研磨机进行研磨、分散，经过滤、真空脱泡、包装，即可得到耐湿热高可靠性环氧导电银胶。
实施例3
本实施例提供了一种耐湿热高可靠性环氧导电银胶的制备方法，其中，该制备方法包括以下步骤：
依次称取双酚A型环氧树脂：12重量份，环氧封端的聚丁二烯橡胶：2重量份，三烯丙基异氰脲酸酯：4.0重量份，环氧改性丙烯酸酯类化合物：1.0重量份，并在高速混料机中将其混合均匀，得到混合物A；
然后向所述得到的混合物A中加入双氰胺：1.0重量份，1-氰乙基-2-乙基-4-甲基咪唑：0.7重量份，过氧化苯甲酰：0.5重量份，气相二氧化硅：0.3重量份，KH-550硅烷偶联剂：0.3重量份，Span80：0.2重量份，在高速混料机中继续将其混合均匀， 得到导电银胶基体B；
最后分批将78重量份的银粉加入到上述制备得到的导电银胶基体B中并充分搅拌，再放入三辊研磨机进行研磨、分散，经过滤、真空脱泡、包装，即可得到耐湿热高可靠性环氧导电银胶。
实施例4
本实施例提供了一种耐湿热高可靠性环氧导电银胶的制备方法，其中，该制备方法包括以下步骤：
依次称取双酚A型环氧树脂：12重量份，环氧封端的聚丁二烯橡胶：2重量份，封闭型1,6-己二异氰酸酯三聚体(六亚甲基二异氰酸酯(HDI)三聚体与苯酚形成的封闭物)：2.0重量份，环氧改性丙烯酸酯类化合物：5.0重量份，并在高速混料机中将其混合均匀，得到混合物A；
然后向所述得到的混合物A中加入双氰胺：1.0重量份，1-氰乙基-2-乙基-4-甲基咪唑：0.7重量份，过氧化苯甲酰：0.5重量份，聚酰胺蜡：0.3重量份，KH-550硅烷偶联剂：0.3重量份，TEGO-0.2重量份，在高速混料机中继续将其混合均匀，得到导电银胶基体B；
最后分批将76重量份的银粉加入到上述制备得到的导电银胶基体B中并充分搅拌，再放入三辊研磨机进行研磨、分散，经过滤、真空脱泡、包装，即可得到耐湿热高可靠性环氧导电银胶。
实施例5
本实施例提供了一种耐湿热高可靠性环氧导电银胶的制备方法，其中，该制备方法包括以下步骤：
依次称取双酚F型环氧树脂：12重量份，超支化聚酯改性增韧剂：2重量份，异氰尿酸三缩水甘油酯：1.0重量份，三烯丙基异氰脲酸酯：3.0重量份，环氧改性丙烯酸酯类化合物：3.0重量份，并在高速混料机中将其混合均匀，得到混合物A；
然后向所述得到的混合物A中加入双氰胺：1.0重量份，2-甲基-4-乙基咪唑：0.7重量份，过氧化苯甲酰：0.5重量份，聚酰胺蜡：0.3重量份，KH-560硅烷偶联剂：0.3重量份，TEGO-245:0.2重量份，并在高速混料机中继续将其混合均匀，得到导电银胶基体B；
最后分批将76重量份的银粉加入到上述制备得到的导电银胶基体B中并充分搅 拌，再放入三辊研磨机进行研磨、分散，经过滤、真空脱泡、包装，即可得到耐湿热高可靠性环氧导电银胶。
对比例1
本对比例提供了一种导电银胶的制备方法，其中，该制备方法包括以下步骤：
依次称取双酚F型环氧树脂：15重量份，环氧封端的聚丁二烯橡胶：3重量份，双氰胺：1.6重量份，有机脲(UR-500)：0.4重量份，1,4-丁二醇二环氧甘油醚：2.0重量份，聚酰胺蜡：0.3重量份，KH-560硅烷偶联剂：0.3重量份，TEGO-245：0.2重量份，并在高速混料机中将其混合均匀，得到混合物A；
然后向所述得到的混合物A中分批加入银粉77.2重量份，继续混合搅拌均匀，得到导电银胶基体；
最后将上述制备的导电银胶基体充分搅拌后放入三辊研磨机进行研磨、分散，再经过滤、真空脱泡、包装，即可得到所述导电银胶。
对比例2
本对比例提供了一种导电银胶的制备方法，其中，该制备方法包括以下步骤：
依次称取双酚F型环氧树脂：13重量份，环氧封端的聚丁二烯橡胶：2重量份，液体芳胺：4.0重量份，2-甲基-4-乙基咪唑：0.7重量份，1,4-丁二醇二环氧甘油醚：2.0重量份，聚酰胺蜡：0.3重量份，KH-560硅烷偶联剂：0.3重量份，TEGO-245：0.2重量份，并在高速混料机中将其混合均匀，得到混合物A；
然后向所述得到的混合物A中分批加入银粉77.5重量份，继续混合搅拌均匀，得到导电银胶基体；
最后将上述制备的导电银胶基体充分搅拌后放入三辊研磨机进行研磨、分散，再经过滤、真空脱泡、包装后，即可得到所述导电银胶。
测试例
为了确定本发明制备得到的耐湿热高可靠性环氧导电银胶的工作性能，现对实施例1-5制备得到的耐湿热高可靠性环氧导电银胶及对比例1、2制备得到的导电银胶分别进行了性能测试分析，测试项目主要包括粘度、存储24h后的粘度、触变指数、玻璃化转变温度、粘结强度、体积电阻率及热分解温度等，上述粘度、触变指数、玻璃化转变温度、粘结强度、体积电阻率及热分解温度等均是采用本领域的常规技术手段进行测量的，相关性能参数请见表1所示。
表1
Figure PCTCN2015098837-appb-000001
高温老化实验：半导体封装中常用的标准回流焊温度为260℃，一般测试3次，每次15秒左右；本申请实施例中在280℃下进行高温老化实验，且测试的次数(5次)更多，每次持续的时间(30s)更长，从表1中可以看出经历更多次、时间更长的高温老化后本申请的导电银胶的粘结强度也没有明显的下降，具有高可靠性。
冷热冲击实验：实验温度为-40℃-150℃，冷热冲击次数为200次，由表1中的实验结果可以看出，冷热冲击对体系的粘结强度基本没有影响。
高温、高湿老化实验：实验温度为85℃，湿度为85％RH，老化时间为168h；从表1中可以看出，本申请的导电银胶在经高温、高湿老化后，其粘结强度也基本没有变化。而对比例1、对比例2制备得到的导电银胶在经湿热老化后，其粘结强度均有明显的下降。
从表1中我们还可以发现，本发明实例1-5制备得到的导电银胶经150℃/90min固化后，其体积电阻率都在l0-4Ω/cm数量级。
综上所述，冷热冲击对体系粘结强度基本没有影响，且高温和湿热老化后，粘结强度也没有明显的下降；反而个别实施例制备得到的导电银胶的粘结强度还有一定程度的提高，这说明本发明制备得到的导电银胶具有较高的可靠性，进而具备十分优异的工作特性，适合半导体芯片的粘结与固定。
另外，将实施例1-5及对比例1、对比例2制备得到的导电银胶存储24小时后，分别测量上述导电银胶的粘度，粘度结果如表1所示，通过粘度的对比可以发现，储24小时后对比实例2制备得到的导电银胶的粘度大幅度增加；对比实例1制备得到的导电银胶的粘度虽然没有变化，但由于其粘度偏大，导致该导电银胶的操作性差，存在拉丝和甩胶的问题。而本发明实例1-5制备得到的导电银胶的粘度适中，储存24小时之后粘度基本没有变化，并且一直保持较低的粘度，这说明本发明制备得到的导电银胶具有良好的操作性，且储存稳定，适用期长，可以满足当前半导体封装的应用要求。

Claims (10)

  1. 一种环氧导电银胶，其中，以所述耐湿热高可靠性环氧导电银胶的总重量为100％计，该耐湿热高可靠性环氧导电银胶是由以下原料制备得到的：65-85wt％的金属银粉，5.0-30wt％的环氧树脂，1-15wt％的具有三嗪结构的活性杂环化合物，0.5-10wt％的丙烯酸树脂，1.0-3.5wt％的固化剂，0.05-1.5wt％的促进剂及0.01-3wt％的功能助剂；
    优选所述原料中还包括1-10wt％的增韧稀释剂；
    还优选所述功能助剂包括消泡剂、分散剂、流平剂、偶联剂和触变剂中的一种或几种的组合。
  2. 根据权利要求1所述的银胶，其中，所述金属银粉选自球形、片状、棒状和树枝状金属银粉中的一种或几种的组合；
    优选所述金属银粉为片状金属银粉与球形金属银粉的组合；
    还优选所述金属银粉的尺寸为0.1-10μm，更优选为0.5-5μm。
  3. 根据权利要求1所述的银胶，其中，所述环氧树脂选自双酚A型环氧树脂、氢化双酚A型环氧树脂、双酚F型环氧树脂、海因环氧树脂、4,4’二氨基二苯甲烷四缩水甘油胺型环氧树脂、三缩水甘油基对氨基苯酚型环氧树脂、4,5-环氧环己烷-1,2-二甲酸二缩水甘油酯环氧树脂、脂环族环氧树脂和酚醛环氧树脂中的一种或几种的组合；
    优选所述脂环族环氧树脂包括3,4-环氧环己烯甲基-3,4-环氧环己烯酸酯、4,5-环氧环己烷-1,2-二甲酸二缩水甘油酯或双((3,4-环氧环己基)甲基)己二酸酯。
  4. 根据权利要求1所述的银胶，其中，所述具有三嗪结构的活性杂环化合物选自1,2,4-三嗪、1,3,5-三嗪、4-氨基-1,3,5-三嗪-2-酮、3-氨基-5-苯基-1,3,5-三嗪、2,4-二氨基-6-苯基-1,3,5-三嗪、六亚甲基二异氰酸酯三聚体及其封闭物、甲苯二异氰酸酯三聚体及其封闭物、异氰尿酸三缩水甘油酯、三烯丙基异氰脲酸酯和氨基取代苯并三嗪类衍生物中的一种或几种的组合；
    优选所述具有三嗪结构的活性杂环化合物包括异氰尿酸三缩水甘油酯或三烯丙基异氰脲酸酯。
  5. 根据权利要求1所述的银胶，其中，所述丙烯酸树脂选自丙烯酸酯预聚物、多官能团丙烯酸树脂、环氧改性丙烯酸树脂、聚氨酯改性丙烯酸树脂、有机硅改性丙 烯酸树脂和超支化聚酯改性丙烯酸树脂中的一种或几种的组合；
    优选所述丙烯酸酯预聚物的官能度≥2，粘度≤10000mPas；
    还优选所述多官能团丙烯酸树脂包括丙烯酸酯基的数目≥2，粘度≤10Pas的丙烯酸树脂。
  6. 根据权利要求1所述的银胶，其中，所述固化剂选自咪唑类固化剂、咪唑改性物类固化剂、芳香族胺类固化剂、双氰胺、双氰胺衍生物类固化剂、有机酸酰肼类固化剂、三氟化硼-胺络合物类固化剂及微胶囊固化剂中的一种或几种的组合；
    优选所述咪唑类固化剂包括2-甲基咪唑、2-苯基咪唑、2-乙基-4-甲基咪唑或1,2-二甲基咪唑；
    还优选所述咪唑改性物类固化剂包括氰乙基改性咪唑类固化剂、长烷基链改性咪唑类固化剂、PN-23、PN-31、PN-40或PN-50；
    更优选所述氰乙基改性咪唑类固化剂包括1-氰乙基-2-乙基-4-甲基咪唑或1-氰乙基-2-苯基咪唑；所述长烷基链改性咪唑类固化剂包括2-十七烷基咪唑或2,4-二氨基-6-(2-十一烷基咪唑基)-1-乙基三嗪；
    还优选所述芳香族胺类固化剂包括4,4’-二氨基二苯甲烷、4,4’-二氨基二苯基砜、间苯二胺、间苯二甲胺或二乙基甲苯二胺；
    还优选所述双氰胺衍生物类固化剂包括3,5-二取代苯胺改性的双氰胺衍生物、间甲苯胺改性的双氰胺或苯肼改性的双氰胺；
    还优选所述有机酸酰肼类固化剂包括琥珀酸酰肼、己二酸二酰肼、癸二酸酰肼、间苯二甲酸酰肼或对羟基安息香酸酰肼；
    还优选所述三氟化硼-胺络合物类固化剂包括三氟化硼与乙胺、哌啶、三乙胺或苯胺形成的络合物。
  7. 根据权利要求1所述的银胶，其中，所述促进剂选自2,4,6-三(二甲氨基甲基)苯酚、2,4,6-三(二甲氨基甲基)苯酚的三(2-乙基己酸)盐、咪唑类化合物及其盐络合物、三苯基膦、四丁基溴化膦、四丁基醋酸膦、四丁基氢氧化膦、苄基三苯基溴化膦、1-氰乙基-2-乙基-4-甲基咪唑、四甲基胍、过氧化苯甲酰、有机脲和乙酰丙酮的金属盐中的一种或几种的组合；
    优选所述乙酰丙酮的金属盐包括乙酰丙酮的铝盐、乙酰丙酮的钴盐、乙酰丙酮的锌盐、乙酰丙酮的铜盐、乙酰丙酮的镍盐、乙酰丙酮的锰盐、乙酰丙酮的铬盐、乙酰 丙酮的钛盐或乙酰丙酮的锆盐。
  8. 根据权利要求1所述的银胶，其中，所述增韧稀释剂选自端羧基液体丁腈橡胶、端羟基液体丁腈橡胶、端氨基液体丁腈橡胶、端环氧基液体丁腈橡胶、端羧基液体聚丁二烯橡胶、端羟基液体聚丁二烯橡胶、环氧封端的聚丁二烯橡胶、液体聚氨酯、核壳橡胶粒子、超支化聚酯、正丁基缩水甘油醚、l,4-丁二醇二缩水甘油醚、三羟甲基丙烷缩水甘油醚、丙三醇三缩水甘油醚、糠醇缩水甘油醚、乙二醇二缩水甘油醚、新戊二醇二缩水甘油醚、烯丙基缩水甘油醚、苯基缩水甘油醚、苄基缩水甘油醚、2-乙基己基缩水甘油醚、C12-C14烷基缩水甘油醚、二乙二醇缩水甘油醚、对叔丁基缩水甘油醚、环已二醇二缩水甘油醚和间苯二酚二缩水甘油醚中的一种或几种的组合。
  9. 权利要求1-8任一项所述的环氧导电银胶的制备方法，其中，该制备方法包括以下步骤：
    a、将环氧树脂、增韧稀释剂、具有三嗪结构的活性杂环化合物及丙烯酸树脂混合均匀，得到混合物A；
    b、向混合物A中依次加入固化剂、促进剂和功能助剂，得到胶体B；
    c、将金属银粉加入到所述胶体B中，搅拌均匀，再经研磨，分散，过滤、真空脱泡、包装，得到所述耐湿热高可靠性环氧导电银胶。
  10. 权利要求1-8任一项所述的环氧导电银胶作为电子元器件的芯片粘结剂的应用及其在电极焊接中的应用。
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