WO2018006503A1 - Silver salt-doped conductive silver adhesive, and preparation method and use thereof - Google Patents

Silver salt-doped conductive silver adhesive, and preparation method and use thereof Download PDF

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Publication number
WO2018006503A1
WO2018006503A1 PCT/CN2016/101131 CN2016101131W WO2018006503A1 WO 2018006503 A1 WO2018006503 A1 WO 2018006503A1 CN 2016101131 W CN2016101131 W CN 2016101131W WO 2018006503 A1 WO2018006503 A1 WO 2018006503A1
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Prior art keywords
silver
weight
parts
curing agent
salt
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PCT/CN2016/101131
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French (fr)
Chinese (zh)
Inventor
孙蓉
韩延康
张保坦
朱朋莉
李刚
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深圳先进技术研究院
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Publication of WO2018006503A1 publication Critical patent/WO2018006503A1/en

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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
    • 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
    • C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
    • C08K13/02—Organic and inorganic ingredients
    • 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
    • C08K3/02—Elements
    • C08K3/08—Metals
    • 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
    • C08K3/16—Halogen-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
    • C08K3/28—Nitrogen-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
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/098—Metal salts of carboxylic acids
    • 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
    • C08K7/00—Use of ingredients characterised by shape
    • 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
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/16—Solid spheres
    • C08K7/18—Solid spheres inorganic
    • 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
    • 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
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C08K2003/0806—Silver
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K

Definitions

  • the invention relates to a conductive silver paste doped with a silver salt, a preparation method and application thereof, and belongs to the technical field of semiconductor materials and preparation thereof.
  • conductive adhesive As a substitute for solder, the traditional packaging material in the field of electronic packaging, conductive adhesive has many advantages, such as: environmentally friendly, no toxic metal, no pre-cleaning and post-weld cleaning in the process; mild curing temperature, greatly reducing the electronic device Thermal damage and internal stress, especially suitable for heat sensitive materials and non-weldable materials; high line resolution, and line resolution below 200 ⁇ m is more suitable for fine pitch manufacturing. Many advantages of conductive adhesives have been adapted to the development trend of miniaturization, thinning and integration of electronic devices, so they are widely used in microelectronic packaging such as IC packaging, LED packaging, solar cells, and RF antennas.
  • the conductive adhesive is generally composed of a resin, a conductive filler and an additive, and is cured or dried to form an adhesive having a certain conductivity, heat conduction, mechanics and the like.
  • conductive glue has replaced tin-lead solder in many electronic fields, it still has some shortcomings, such as high volume resistivity, insufficient bonding strength, and poor storage and transportation performance. Therefore, in order to improve the electrical conductivity of the conductive adhesive, the content of the metal filler is often increased (65%-90%). Although increasing the content of the metal filler can increase its conductivity to some extent, it is also due to the decrease of the resin content.
  • the conductive adhesive loses part of the mechanical properties, and at the same time, the viscosity of the conductive adhesive increases, the bond strength and the handling performance are lowered, and the cost of the conductive adhesive is greatly increased.
  • nano-fillers researchers introduced one or more of nano-silver wires, silver nanoparticles, silver nano-sheets, carbon nanotubes, graphene, etc. into conductive paste, due to the formation of new conductive pathways or The sintering of the nano-conductive filler during the curing process greatly reduces the contact resistance between the original conductive fillers, and a small amount of silver powder can be used to achieve a small volume resistivity.
  • an object of the present invention is to provide a method for preparing a conductive silver paste doped with a silver salt.
  • Another object of the present invention is to provide a silver salt-doped conductive silver paste prepared by the above method for preparing a silver salt-doped conductive silver paste.
  • the present invention provides a conductive silver paste doped with a silver salt, which is prepared from the following materials:
  • Curing agent 0.5 to 60 parts by weight
  • Coupling agent 0.05 to 5 parts by weight
  • Anti-precipitation agent 0.05 to 2 parts by weight.
  • the silver salt-doped conductive silver paste according to the present invention is prepared by the following steps:
  • the silver salt comprises one or a combination of silver nitrate, silver acetate, and silver halide.
  • the silver halide used may be one or a combination of silver fluoride, silver chloride, silver bromide and silver iodide. .
  • the micron silver powder is selected from one or a combination of a sheet-like, spherical and rod-shaped silver powder having a size of 1 to 10 ⁇ 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 kinds of silver powders” involved in the present invention may be a combination of several kinds of silver powders according to any suitable ratio.
  • the present invention does not require the proportional relationship between the amounts of the silver powders, and those skilled in the art can perform on-site operations. Need to choose the appropriate dosage ratio relationship, however, it should be noted that the sum of the above-mentioned several kinds of micron silver powder 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 disclosed in the prior art which is applicable to the preparation of conductive silver paste; preferably, the Epoxy resin includes bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, bisphenol F epoxy resin, hydan epoxy resin, high temperature resistant AG-80/90 epoxy resin, TDE-85 ring A combination of one or more of an oxyresin, an alicyclic epoxy resin, and a novolac 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 groups disclosed in the prior art which can be applied to the preparation of the conductive silver paste.
  • Epoxy resins can be used in the present invention; in a specific embodiment of the invention, the cycloaliphatic epoxy resin comprises 3,4-epoxycyclohexenemethyl-3,4-epoxycyclohexenoate , 4,5-epoxycyclohexane-1,2-dicarboxylic acid diglycidyl ester or bis((3,4-epoxycyclohexyl)methyl) adipate, epoxy-269, epoxy- 206, epoxy-201 (produced by AkzoNobel) and the like.
  • the hydantoin used is a conventional product in the art, and any of the hydantoins disclosed in the prior art which can be applied to the preparation of the conductive silver paste. Resins 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 applied to the preparation of the conductive silver paste is It can be used in the present invention; in a specific embodiment of the present invention, the phenolic epoxy resin comprises a phenolic epoxy resin of the type EPALOLD-8240 produced by Emerald Company of the United States; and the model of NPPN produced by Taiwan Nanya Plastic Industry Co., Ltd. -631 of phenolic epoxy resin; Dow Chemical (DOW) model DEN431, DEN438 phenolic epoxy resin; Guangzhou Kailuo Chemical Co., Ltd. produced model F-51 phenolic epoxy resin.
  • the phenolic epoxy resin comprises a phenolic epoxy resin of the type EPALOLD-8240 produced by Emerald Company of the United States; and the model of NPPN produced by Taiwan Nanya Plastic Industry Co., Ltd. -631 of phenolic epoxy resin; Dow Chemical (DOW) model DEN431, DEN438 phenolic epoxy resin;
  • the bisphenol F-type epoxy resin used is a conventional substance used in the art, and in a specific embodiment of the present invention, it comprises a Dow produced by the United States. Model DER354 bisphenol F epoxy resin.
  • the curing agent used in the present invention may be any curing agent disclosed in the prior art which is suitable for the conductive silver paste; preferably, the curing agent includes Imidazole curing agent, imidazole modified curing agent, aromatic amine curing agent, aromatic amine modified curing agent, dicyandiamide curing agent, dicyandiamide derivative curing agent, acid anhydride curing agent a combination of one or more of an organic acid hydrazide curing agent, a boron trifluoride-amine complex curing agent, a polyamine salt curing agent, and a microencapsulated curing agent;
  • the curing agent is a dicyandiamide-based curing agent or a dicyandiamide derivative-based curing agent.
  • the "combination of several curing agents” involved in the present invention may be several curing agents in any suitable ratio.
  • the combination of the lines, the present invention does not require the proportional relationship between the amounts of the curing agents, and those skilled in the art can select the appropriate dosage ratio according to the needs of the field operation, but it should be noted that the above several curing agents The sum of the amounts used needs to meet the limits of the amount of raw materials used in the present invention.
  • the imidazole curing agent used in the present invention is a material conventional in the art.
  • the imidazole curing agent includes 2-methylimidazole, 2-phenylimidazole, 2-ethyl-4-methyl Imidazole or 1,2-dimethylimidazole.
  • the imidazole modified type curing agent used in the present invention is a material conventional in the art.
  • the imidazole modified substance curing agent comprises a cyanoethyl modified imidazole curing agent, a long alkyl group. Chain modified imidazole curing agent, imidazole modified curing agent BMI, 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 long alkyl chain-modified imidazole curing agent of the type C17Z produced 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-based curing agent used in the present invention is a conventional one in the art, and the aromatic amine-based curing agent includes 4,4'-methylenediphenylamine, p-aminophenol, 4,4'-diaminodiphenyl. Methane, 4,4'-diaminodiphenyl sulfone, m-phenylenediamine, m-xylylenediamine or diethyltoluenediamine; the aromatic amine modified type curing agent includes halogenated phenol, acylation Phenol and sulfonated phenol.
  • 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 A dicyandiamide or benzoquinone-modified dicyandiamide; in a specific 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 acid anhydride type curing agent used in the present invention is a substance conventionally known in the art, and the acid anhydride type curing agent includes phthalic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride glyceride, polysebacic anhydride, and tung oil anhydride. Methyl hexahydrophthalic anhydride.
  • the organic acid hydrazide-based curing agent used in the present invention is a substance conventionally known in the art, and the organic acid hydrazide-based curing agent includes succinic acid hydrazide, adipic acid dihydrazide, sebacic acid dihydrazide, and isophthalic acid.
  • succinic acid hydrazide adipic acid dihydrazide
  • sebacic acid dihydrazide sebacic acid dihydrazide
  • POBH p-hydroxybenzoic acid hydrazide
  • 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 polyamine salt curing agent used in the present invention is a substance conventionally known in the art, and the polyamine salt curing agent includes a polyhydroxy acid salt of a hydroxy acid and the like.
  • 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.
  • HX3941HP poly polyamine modified imidazole microcapsule curing agent and ZHJ-1 thermal control microcapsule epoxy curing agent successfully developed by the School of Chemistry and Life Sciences of Central South University for Nationalities.
  • the promoter comprises 2,4,6-tris(dimethylaminomethyl)phenol, 2-ethyl-4-methylimidazole, Triphenylphosphine, 1-cyanoethyl-2-ethyl-4-methylimidazole, N,N-dimethylcyclohexylamine, N,N-dimethylbenzylamine, organic urea, tetramethylguanidine
  • a metal salt of acetylacetone, dibenzoyl peroxide and aryl isocyanate 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 silver-doped conductive silver paste according to the present invention, the organic urea promoter used is a conventional substance in the art, and specifically includes N-p-chlorophenyl-N,N'-dimethylurea, dimethyl
  • the type of imidazole urea, Evonik Degussa produced by UR-200, UR-300 and UR-500, and the model produced by Emerald Performance Materials LLC are OMICURE U- Organic urea of 24M, OMICURE U-35M, OMICURE U-52M and OMICURE U-405M.
  • the metal salt of acetylacetone used is a product commonly used in the art.
  • the metal salt of acetylacetone comprises an aluminum salt of acetylacetone.
  • the coupling agent comprises a silane coupling agent, a titanate coupling agent, an aluminate coupling agent, a bimetallic coupling agent, and wood.
  • a coupling agent and a tin coupling agent are preferably silane coupling agent, a titanate coupling agent, an aluminate coupling agent, a bimetallic coupling agent, and wood.
  • the "combination of several coupling agents” involved in the present invention may be a combination of several coupling agents in any suitable ratio, and the present invention does not require a ratio relationship between the coupling agents.
  • the skilled person can select the appropriate dosage ratio according to the needs of the field operation, but it should be noted that the sum of the above-mentioned several coupling agents needs to meet the limit of the amount of the raw materials of the present invention.
  • the silane coupling agent is a conventional substance in the art, and includes ⁇ -aminopropyltriethoxysilane and ⁇ -aminopropyltrimethoxysilane (such as Nanjing Qianjin Chemical Co., Ltd. Co., Ltd.
  • KH-550 coupling agent produces KH-550 coupling agent), ⁇ -(2,3-epoxypropoxy)propyltrimethoxysilane (such as KH-560 produced by Nanjing Qianjin Chemical Co., Ltd.) Coupling agent), ⁇ -(ethylenediamine)propyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, ⁇ -(methacryloyloxy)propyl Trimethoxysilane (such as KH-570 coupling agent produced by Nanjing Forward Chemical Co., Ltd.) and ⁇ -mercaptopropyltrimethoxysilane (such as KH-590 produced by Nanjing Qianjin Chemical Co., Ltd.) Coupling agent);
  • the titanate coupling agent used is conventional in the art and includes isopropyl tris(isostearyl) titanate, isopropyl tris(dodecylbenzenesulfonyl) titanate and isopropyl Base three (dioctyl pyrophosphoryloxy) titanate TMC-201;
  • the aluminate coupling agent used is a conventional material in the art, which comprises distearyloxyisopropylaluminate or aluminate coupling agent F-1 (such as produced by Henan Jiyuan Kehui Material Co., Ltd.). The product).
  • the bimetallic coupling agent used is a conventional material in the art, and includes a zirconium aluminum bimetallic coupling agent TPM (such as a product produced by Yangzhou Lida Resin Co., Ltd.).
  • the lignin coupling agent and the tin coupling agent used in the present invention are also conventional materials used in the art, and those skilled in the art can select a suitable lignin coupling agent and a tin coupling agent according to the needs of the field operation, as long as The purpose of coupling can be achieved.
  • the diluent comprises n-butyl glycidyl ether, 1,4-butanediol diglycidyl ether, trimethylolpropane glycidyl ether , glycerol triglycidyl ether, sterol glycidyl ether, ethylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, allyl glycidyl ether, phenyl glycidyl ether, benzyl glycidyl ether, 2-ethylhexyl glycidyl ether, C12/14 alkyl glycidyl ether, A combination of one or more of diethylene glycol glycidyl ether, p-tert-butyl glycidyl ether, cyclohexanediol diglycidyl ether, trimethylolpropane glycidy
  • the "combination of several diluents" referred to in the present invention may be a combination of several diluents in any suitable ratio, and the present invention does not require a proportional relationship between the amounts of these diluents, 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 diluents needs to meet the limit of the amount of raw materials used in the present invention.
  • the anti-precipitating agent comprises fumed silica and/or organic bentonite.
  • the anti-precipitation agent is a combination of fumed silica and organic bentonite
  • the present invention does not require a proportional relationship between the two substances, 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 sum of the amounts of the two needs to meet the limit of the amount of raw materials used in the present invention.
  • the present invention also provides a method for preparing the above-mentioned silver salt-doped conductive silver paste, which comprises the following steps:
  • the method for preparing a silver salt-doped conductive silver paste according to the present invention wherein the silver salt-doped conductive silver paste is prepared at room temperature;
  • the present invention has no specific requirements for the order of addition of the diluent, the anti-precipitating agent, the coupling agent, the curing agent, and the accelerator in the step (2).
  • Curing agent 0.5 to 60 parts by weight
  • Coupling agent 0.05 to 5 parts by weight
  • Anti-precipitation agent 0.05 to 2 parts by weight.
  • the silver salt comprises one or a combination of silver nitrate, silver acetate, silver halide.
  • micron silver powder is selected from the group consisting of one or a combination of a sheet-shaped, spherical and rod-shaped silver powder having a size of 1 to 10 ⁇ m. .
  • the epoxy resin comprising a bisphenol A type epoxy resin, a hydrogenated bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a sea A combination of one or more of epoxy resin, high temperature resistant AG-80/90 epoxy resin, TDE-85 epoxy resin, alicyclic epoxy resin, and novolac epoxy resin.
  • the curing agent includes an imidazole curing agent, an imidazole modified curing agent, an aromatic amine curing agent, and an aromatic amine modified product.
  • the method for preparing a silver salt-doped conductive silver paste according to the present invention wherein the promoter comprises 2,4,6-tris(dimethylaminomethyl)phenol, 2-ethyl-4-methylimidazole, Triphenylphosphine, 1-cyanoethyl-2-ethyl-4-methylimidazole, N,N-dimethylcyclohexylamine, N,N-dimethylbenzylamine, organic urea, tetramethylguanidine, A combination of one or more of a metal salt of acetylacetone, dibenzoyl peroxide, and aryl isocyanate.
  • the promoter comprises 2,4,6-tris(dimethylaminomethyl)phenol, 2-ethyl-4-methylimidazole, Triphenylphosphine, 1-cyanoethyl-2-ethyl-4-methylimidazole, N,N-dimethylcyclohexylamine, N,N-dimethyl
  • the coupling agent comprises a silane coupling agent, a titanate coupling agent, an aluminate coupling agent, a bimetallic coupling agent, and a wood A combination of one or more of a coupling agent and a tin coupling agent.
  • a method for preparing a silver salt-doped conductive silver paste according to the present invention comprising n-butyl glycidyl ether, 1,4-butanediol diglycidyl ether, trimethylolpropane glycidyl ether , glycerol triglycidyl ether, sterol glycidyl ether, ethylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, allyl glycidyl ether, phenyl glycidyl ether, benzyl glycidyl ether, 2-ethylhexyl glycidyl ether, C12/14 alkyl glycidyl ether, diethylene glycol glycidyl ether, p-tert-butyl glycidyl ether, cyclohexanediol diglycidyl ether, n
  • the anti-precipitation agent comprises fumed silica and/or organic bentonite.
  • the method for preparing a silver salt-doped conductive silver paste according to the present invention wherein the uniform dispersion of the silver salt in the epoxy resin in the step (1) can be achieved by stirring and grinding, thereby obtaining a base resin having uniform composition.
  • the method for preparing a silver salt-doped conductive silver paste according to the present invention wherein the grinding uniformly described in the step (2) can be achieved by a three-roll mill, and then mixed and defoamed to obtain a uniform composition.
  • Base resin B Base resin
  • the method for preparing a silver salt-doped conductive silver paste according to the present invention wherein the polishing in the step (3) can be uniformly performed by a three-roll mill, and then mixed and defoamed to obtain a paste-like doping.
  • Conductive silver paste of silver salt can be uniformly performed by a three-roll mill, and then mixed and defoamed to obtain a paste-like doping.
  • the present invention also provides the use of the above-mentioned silver salt-doped conductive silver paste as a semiconductor electronic packaging material.
  • the preparation method of the invention introduces the silver salt into the conductive silver glue formulation in a doping manner, and can reduce the use amount of the silver powder by 15%-20% under the premise of ensuring the conductive property of the conductive silver glue; when the same silver powder is added, The conductivity of the conductive silver glue is greatly improved, and the conductive silver glue has good shear strength and aging resistance; in addition, the method is simple and easy, the raw material used is lower in price, and the cost of the conductive silver glue is reduced.
  • the prepared silver salt-doped conductive silver paste can be widely used in the fields of solar cells, ICs, and LED packages.
  • the present invention introduces a silver salt into the conductive silver paste formulation in a doped manner, and the introduced small amount of silver salt can greatly improve the electrical conductivity of the conductive adhesive, reduce the percolation threshold of the conductive adhesive, and greatly reduce the amount of silver powder used.
  • the volume resistivity is generally in the range of 10 -5 , which is similar to the silver-doped conductive silver paste prepared by the present invention, but the bonding strength thereof is not up to 20 MPa, which is significantly lower than the conductive silver doped with the silver salt of the present invention.
  • the bonding strength of the glue can be up to 25 MPa), and since the silver salt doped by the present invention is not nano-scale, the silver-doped conductive silver paste prepared by the invention does not have the nano-filler easy to agglomerate and is expensive. Disadvantages; therefore, the preparation method of the invention is convenient and practical, and has great significance for improving the comprehensive performance of the conductive silver paste and reducing the production cost.
  • This embodiment provides a conductive silver paste doped with a silver salt, which is prepared from the following materials:
  • Silver salt (silver nitrate) 0.6 parts by weight;
  • Micron silver powder (mixed sheet-like silver powder, average particle diameter 5 microns) 80 parts by weight;
  • Epoxy resin Shell bisphenol A type epoxy resin 828E 17 parts by weight;
  • Curing agent (dicyandiamide) 1 part by weight
  • Anti-precipitation agent (fumed silica) 0.05 parts by weight;
  • the preparation method of the above silver salt-doped conductive silver paste comprises the following steps:
  • the silver nitrate is filled into the epoxy resin according to the ratio, stirred and ground, so that the silver salt is sufficiently dispersed to form a base resin A having a uniform composition;
  • Base resin B (2) adding a diluent, an anti-precipitating agent, a coupling agent, a curing agent, and a promoter to the base resin A in the above ratio, mixing and then uniformly grinding with a three-roll mill, mixing and defoaming to prepare a uniform composition.
  • Base resin B
  • This embodiment provides a conductive silver paste doped with a silver salt, which is prepared from the following materials:
  • Silver salt (silver nitrate) 0.6 parts by weight;
  • Micron silver powder (mixed sheet-like silver powder, average particle diameter 5 ⁇ m) 70 parts by weight;
  • Epoxy resin Shell bisphenol A type epoxy resin 828E 25.0 parts by weight;
  • Curing agent (dicyandiamide) 1.4 parts by weight;
  • Coupling agent (KH-560) 0.15 parts by weight;
  • Anti-precipitation agent (fumed silica) 0.075 parts by weight;
  • the preparation method of the above silver salt-doped conductive silver paste comprises the following steps:
  • the silver nitrate is filled into the epoxy resin according to the ratio, stirred and ground, so that the silver salt is sufficiently dispersed to form a base resin A having a uniform composition;
  • Base resin B (2) adding a diluent, an anti-precipitating agent, a coupling agent, a curing agent, and a promoter to the base resin A in the above ratio, mixing and then uniformly grinding with a three-roll mill, mixing and defoaming to prepare a uniform composition.
  • Base resin B
  • the silver powder is added to the base resin B in the above ratio, uniformly mixed, and then ground by a three-roll mill, and mixed and defoamed to form a paste-like conductive silver paste-doped conductive silver paste.
  • This embodiment provides a conductive silver paste doped with a silver salt, which is prepared from the following materials:
  • Silver salt (silver nitrate) 0.6 parts by weight;
  • Micron silver powder (mixed sheet-like silver powder, average particle diameter 5 microns) 60 parts by weight;
  • Epoxy resin Shell bisphenol A type epoxy resin 828E 34 parts by weight;
  • Curing agent (dicyandiamide) 2 parts by weight
  • Coupling agent (KH-560) 0.2 parts by weight;
  • Anti-precipitation agent (fumed silica) 0.1 part by weight;
  • the preparation method of the above silver salt-doped conductive silver paste comprises the following steps:
  • the silver nitrate is filled into the epoxy resin according to the ratio, stirred and ground, so that the silver salt is sufficiently dispersed to form a base resin A having a uniform composition;
  • Base resin B (2) adding a diluent, an anti-precipitating agent, a coupling agent, a curing agent, and a promoter to the base resin A in the above ratio, mixing and then uniformly grinding with a three-roll mill, mixing and defoaming to prepare a uniform composition.
  • Base resin B
  • the silver powder is added to the base resin B in the above ratio, uniformly mixed, and then ground by a three-roll mill, and mixed and defoamed to form a paste-like conductive silver paste-doped conductive silver paste.
  • This embodiment provides a conductive silver paste doped with a silver salt, which is prepared from the following materials:
  • Silver salt (silver bromide) 0.6 parts by weight
  • Micron silver powder (mixed sheet-like silver powder, average particle diameter 5 microns) 80 parts by weight;
  • Epoxy resin Shell bisphenol A type epoxy resin 828E 17 parts by weight;
  • Curing agent (dicyandiamide) 1 part by weight
  • Anti-precipitation agent (fumed silica) 0.05 parts by weight;
  • the preparation method of the above silver salt-doped conductive silver paste comprises the following steps:
  • the silver bromide is filled into the epoxy resin according to the ratio, stirred and ground, so that the silver salt is sufficiently dispersed to form a base resin A having a uniform composition;
  • Base resin B (2) adding a diluent, an anti-precipitating agent, a coupling agent, a curing agent, and a promoter to the base resin A in the above ratio, mixing and then uniformly grinding with a three-roll mill, mixing and defoaming to prepare a uniform composition.
  • Base resin B
  • the silver powder is added to the base resin B in the above ratio, uniformly mixed, and then ground by a three-roll mill, and mixed and defoamed to form a paste-like conductive silver paste-doped conductive silver paste.
  • This embodiment provides a conductive silver paste doped with a silver salt, which is prepared from the following materials:
  • Silver salt (silver acetate) 0.6 parts by weight;
  • Micron silver powder (mixed sheet-like silver powder, average particle diameter 5 microns) 80 parts by weight;
  • Epoxy resin Shell bisphenol A type epoxy resin 828E 17 parts by weight;
  • Curing agent (dicyandiamide) 1 part by weight
  • Anti-precipitation agent (fumed silica) 0.05 parts by weight;
  • the preparation method of the above silver salt-doped conductive silver paste comprises the following steps:
  • the silver acetate is filled into the epoxy resin according to the ratio, stirred and ground, so that the silver salt is sufficiently dispersed to form a base resin A having a uniform composition
  • Base resin B (2) adding a diluent, an anti-precipitating agent, a coupling agent, a curing agent, and a promoter to the base resin A in the above ratio, mixing and then uniformly grinding with a three-roll mill, mixing and defoaming to prepare a uniform composition.
  • Base resin B
  • the silver powder is added to the base resin B in the above ratio, uniformly mixed, and then ground by a three-roll mill, and mixed and defoamed to form a paste-like conductive silver paste-doped conductive silver paste.
  • Micron silver powder (mixed sheet-like silver powder, average particle diameter 5 microns) 80 parts by weight;
  • Epoxy resin Shell bisphenol A epoxy resin 828E 17.6 parts by weight;
  • Curing agent (dicyandiamide) 1 part by weight
  • Anti-precipitation agent (fumed silica) 0.05 parts by weight;
  • the preparation method of the above silver salt-doped conductive silver paste comprises the following steps:
  • This embodiment provides a conductive silver paste doped with a silver salt, which is prepared from the following materials:
  • Silver salt (silver nitrate) 0.6 parts by weight;
  • Micron silver powder (mixed sheet-like silver powder, average particle diameter 5 microns) 80 parts by weight;
  • Curing agent (4,4'-methylenediphenylamine) 4.0 parts by weight;
  • Anti-precipitation agent (fumed silica) 0.05 parts by weight;
  • the preparation method of the above silver salt-doped conductive silver paste comprises the following steps:
  • the silver nitrate is filled into the epoxy resin according to the ratio, stirred and ground, so that the silver salt is sufficiently dispersed to form a base resin A having a uniform composition;
  • Base resin B (2) adding a diluent, an anti-precipitating agent, a coupling agent, a curing agent, and a promoter to the base resin A in the above ratio, mixing and then uniformly grinding with a three-roll mill, mixing and defoaming to prepare a uniform composition.
  • Base resin B
  • the silver powder is added to the base resin B in the above ratio, uniformly mixed, and then ground by a three-roll mill, and mixed and defoamed to form a paste-like conductive silver paste-doped conductive silver paste.
  • This embodiment provides a conductive silver paste doped with a silver salt, which is prepared from the following materials:
  • Silver salt (silver bromide) 0.6 parts by weight
  • Micron silver powder (mixed sheet-like silver powder, average particle diameter 5 microns) 80 parts by weight;
  • Curing agent (4,4'-methylenediphenylamine) 4.0 parts by weight;
  • Anti-precipitation agent (fumed silica) 0.05 parts by weight;
  • the preparation method of the above silver salt-doped conductive silver paste comprises the following steps:
  • the silver bromide is filled into the epoxy resin according to the ratio, stirred and ground, so that the silver salt is sufficiently dispersed to form a base resin A having a uniform composition;
  • Base resin B (2) adding a diluent, an anti-precipitating agent, a coupling agent, a curing agent, and a promoter to the base resin A in the above ratio, mixing and then uniformly grinding with a three-roll mill, mixing and defoaming to prepare a uniform composition.
  • Base resin B
  • the silver powder is added to the base resin B in the above ratio, uniformly mixed, and then ground by a three-roll mill, and mixed and defoamed to form a paste-like conductive silver paste-doped conductive silver paste.
  • This embodiment provides a conductive silver paste doped with a silver salt, which is prepared from the following materials:
  • Silver salt (silver acetate) 0.6 parts by weight;
  • Micron silver powder (mixed sheet-like silver powder, average particle diameter 5 microns) 80 parts by weight;
  • Curing agent (4,4'-methylenediphenylamine) 4.0 parts by weight;
  • Anti-precipitation agent (fumed silica) 0.05 parts by weight;
  • the preparation method of the above silver salt-doped conductive silver paste comprises the following steps:
  • the silver acetate is filled into the epoxy resin according to the ratio, stirred and ground, so that the silver salt is sufficiently dispersed to form a base resin A having a uniform composition
  • Base resin B (2) adding a diluent, an anti-precipitating agent, a coupling agent, a curing agent, and a promoter to the base resin A in the above ratio, mixing and then uniformly grinding with a three-roll mill, mixing and defoaming to prepare a uniform composition.
  • Base resin B
  • the silver powder is added to the base resin B in the above ratio, uniformly mixed, and then ground by a three-roll mill, and mixed and defoamed to form a paste-like conductive silver paste-doped conductive silver paste.
  • Micron silver powder (mixed sheet-like silver powder, average particle diameter 5 microns) 80 parts by weight;
  • Curing agent (4,4'-methylenediphenylamine) 4.0 parts by weight;
  • Anti-precipitation agent (fumed silica) 0.05 parts by weight;
  • the preparation method of the above silver salt-doped conductive silver paste comprises the following steps:
  • This embodiment provides a conductive silver paste doped with a silver salt, which is prepared from the following materials:
  • Silver salt (silver nitrate) 0.6 parts by weight;
  • Micron silver powder (mixed sheet-like silver powder, average particle diameter 5 microns) 80 parts by weight;
  • Epoxy resin (DER354) 9.0 parts by weight
  • Curing agent (methyl hexahydrophthalic anhydride) 9.0 parts by weight;
  • Anti-precipitation agent (fumed silica) 0.1 part by weight;
  • the preparation method of the above silver salt-doped conductive silver paste comprises the following steps:
  • the silver nitrate is filled into the epoxy resin according to the ratio, stirred and ground, so that the silver salt is sufficiently dispersed to form a base resin A having a uniform composition;
  • Base resin B (2) adding a diluent, an anti-precipitating agent, a coupling agent, a curing agent, and a promoter to the base resin A in the above ratio, mixing and then uniformly grinding with a three-roll mill, mixing and defoaming to prepare a uniform composition.
  • Base resin B
  • the silver powder is added to the base resin B in the above ratio, uniformly mixed, and then ground by a three-roll mill, and mixed and defoamed to form a paste-like conductive silver paste-doped conductive silver paste.
  • This embodiment provides a conductive silver paste doped with a silver salt, which is prepared from the following materials:
  • Silver salt (silver bromide) 0.6 parts by weight
  • Micron silver powder (mixed sheet-like silver powder, average particle diameter 5 microns) 80 parts by weight;
  • Epoxy resin (DER354) 9.0 parts by weight
  • Curing agent (methyl hexahydrophthalic anhydride) 9.0 parts by weight;
  • Anti-precipitation agent (fumed silica) 0.1 part by weight;
  • the preparation method of the above silver salt-doped conductive silver paste comprises the following steps:
  • the silver bromide is filled into the epoxy resin according to the ratio, stirred and ground, so that the silver salt is sufficiently dispersed to form a base resin A having a uniform composition;
  • Base resin B (2) adding a diluent, an anti-precipitating agent, a coupling agent, a curing agent, and a promoter to the base resin A in the above ratio, mixing and then uniformly grinding with a three-roll mill, mixing and defoaming to prepare a uniform composition.
  • Base resin B
  • the silver powder is added to the base resin B in the above ratio, uniformly mixed, and then ground by a three-roll mill, and mixed and defoamed to form a paste-like conductive silver paste-doped conductive silver paste.
  • This embodiment provides a conductive silver paste doped with a silver salt, which is prepared from the following materials:
  • Silver salt (silver acetate) 0.6 parts by weight;
  • Micron silver powder (mixed sheet-like silver powder, average particle diameter 5 microns) 80 parts by weight;
  • Epoxy resin (DER354) 9.0 parts by weight
  • Curing agent (methyl hexahydrophthalic anhydride) 9.0 parts by weight;
  • Anti-precipitation agent (fumed silica) 0.1 part by weight;
  • the preparation method of the above silver salt-doped conductive silver paste comprises the following steps:
  • the silver acetate is filled into the epoxy resin according to the ratio, stirred and ground, so that the silver salt is sufficiently dispersed to form a base resin A having a uniform composition
  • Base resin B (2) adding a diluent, an anti-precipitating agent, a coupling agent, a curing agent, and a promoter to the base resin A in the above ratio, mixing and then uniformly grinding with a three-roll mill, mixing and defoaming to prepare a uniform composition.
  • Base resin B
  • the silver powder is added to the base resin B in the above ratio, uniformly mixed, and then ground by a three-roll mill, and mixed and defoamed to form a paste-like conductive silver paste-doped conductive silver paste.
  • Micron silver powder (mixed sheet-like silver powder, average particle diameter 5 microns) 80 parts by weight;
  • Epoxy resin (DER354) 9.3 parts by weight
  • Curing agent (methyl hexahydrophthalic anhydride) 9.3 parts by weight;
  • Anti-precipitation agent (fumed silica) 0.1 part by weight;
  • the preparation method of the above silver salt-doped conductive silver paste comprises the following steps:
  • This embodiment provides a conductive silver paste doped with a silver salt, which is prepared from the following materials:
  • Silver salt (silver acetate) 0.2 parts by weight;
  • Micron silver powder (mixed sheet-like silver powder, average particle diameter 5 microns) 80 parts by weight;
  • Epoxy resin (DER354) 9.2 parts by weight
  • Curing agent (methyl hexahydrophthalic anhydride) 9.2 parts by weight;
  • Anti-precipitation agent (fumed silica) 0.1 part by weight;
  • the preparation method of the above silver salt-doped conductive silver paste comprises the following steps:
  • the silver acetate is filled into the epoxy resin according to the ratio, stirred and ground, so that the silver salt is sufficiently dispersed to form a base resin A having a uniform composition
  • Base resin B (2) adding a diluent, an anti-precipitating agent, a coupling agent, a curing agent, and a promoter to the base resin A in the above ratio, mixing and then uniformly grinding with a three-roll mill, mixing and defoaming to prepare a uniform composition.
  • Base resin B
  • the silver powder is added to the base resin B in the above ratio, uniformly mixed, and then ground by a three-roll mill, and mixed and defoamed to form a paste-like conductive silver paste-doped conductive silver paste.
  • This embodiment provides a conductive silver paste doped with a silver salt, which is prepared from the following materials:
  • Silver salt (silver acetate) 0.4 parts by weight;
  • Micron silver powder (mixed sheet-like silver powder, average particle diameter 5 microns) 80 parts by weight;
  • Epoxy resin (DER354) 9.1 parts by weight
  • Curing agent (methyl hexahydrophthalic anhydride) 9.1 parts by weight;
  • Anti-precipitation agent (fumed silica) 0.1 part by weight;
  • the preparation method of the above silver salt-doped conductive silver paste comprises the following steps:
  • the silver acetate is filled into the epoxy resin according to the ratio, stirred and ground, so that the silver salt is sufficiently dispersed to form a base resin A having a uniform composition
  • the silver powder is added to the base resin B in the above ratio, uniformly mixed, and then ground by a three-roll mill, and mixed and defoamed to form a paste-like conductive silver paste-doped conductive silver paste.
  • This embodiment provides a conductive silver paste doped with a silver salt, which is prepared from the following materials:
  • Micron silver powder (mixed sheet-like silver powder, average particle diameter 5 microns) 80 parts by weight;
  • Epoxy resin Shell bisphenol A type epoxy resin 828E 17 parts by weight;
  • Curing agent (dicyandiamide) 1 part by weight
  • Anti-precipitation agent (fumed silica) 0.05 parts by weight;
  • the preparation method of the above silver salt-doped conductive silver paste comprises the following steps:
  • a mixed silver salt composed of silver bromide and silver nitrate is filled into the epoxy resin according to the ratio, stirred and ground, so that the silver salt is sufficiently dispersed to form a base resin A having a uniform composition;
  • Base resin B (2) adding a diluent, an anti-precipitating agent, a coupling agent, a curing agent, and a promoter to the base resin A in the above ratio, mixing and then uniformly grinding with a three-roll mill, mixing and defoaming to prepare a uniform composition.
  • Base resin B
  • the special effect between the silver salt and the silver powder compensates for the defects on the surface of the silver powder, and at the same time, the silver salt nanoclusters are formed, and the path between the conductive fillers is increased. Moreover, the oxidation of the surface of the silver powder by oxygen is effectively prevented, and the reliability is greatly improved; in order to determine the working performance of the conductive silver paste prepared by the present invention, the applicant also separately performs the conductive silver paste prepared in the examples 1-17. Test analysis, the test results are shown in Table 1.
  • the micron silver powder required is greatly reduced (reduced by about 20% by weight) compared to the product not doped with the silver salt (as compared with Examples 3 and 6), achieving the same conductivity.
  • the volume resistivity of the conductive silver paste can reach 10 -5 orders of magnitude when the silver powder is filled at 70% and 80%, which has reached the higher level of the currently available conductive silver paste (currently available in the market for conductive silver)
  • the volume resistivity of glues such as WTS-5101/5102/5106 and DK901 is generally on the order of 10 -4 ; and the shear strength of the product is improved to some extent while reducing the amount of conductive filler, as in Examples 1-3.
  • the shear strength of the prepared product is increased from 23.10 MPa to 25.21 MPa; in addition, the doping of the silver salt can also lower the percolation threshold of the conductive silver paste.
  • the percolation threshold of the prepared conductive silver paste can be reduced from 15% to 6%.
  • the silver salt doped conductive silver paste can have high conductivity and bond strength by using the simple and easy way of doping with silver salt, and the method can also greatly save production cost and improve.
  • the market competitiveness of the products, the prepared silver salt-doped conductive silver paste can be widely used in the fields of solar cells, ICs and LED packages.

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Abstract

Provided are a silver salt-doped conductive silver adhesive, and a preparation method and a use thereof. The silver salt-doped conductive silver adhesive is prepared and obtained from the following raw materials: 0.01-5 parts by weight of a silver salt, 50-85 parts by weight of a micron silver powder, 10-50 parts by weight of an epoxy resin, 0.5-60 parts by weight of a curing agent, 0.05-5 parts by weight of an accelerator, 0.05-5 parts by weight of a coupling agent, 1-10 parts by weight of a diluent and 0.05-2 parts by weight of an anti-precipitant. In the preparation method of the present invention, the silver salt is introduced into a formula of the conductive silver adhesive in a doping manner, so that the amount of the silver powder can be reduced by 15%-20% on the premise of ensuring the conductive performance of the conductive silver adhesive. When the addition amount of the silver powder is the same, the electrical conductivity of the conductive silver adhesive is greatly improved, and the conductive silver adhesive has a good shear strength and an aging resistance. The silver salt-doped conductive silver adhesive prepared and obtained can be widely applied to the following fields: solar cells, IC and LED packaging, etc.

Description

一种掺杂银盐的导电银胶及其制备方法与应用Conductive silver glue doped with silver salt and preparation method and application thereof 技术领域Technical field
本发明涉及一种掺杂银盐的导电银胶及其制备方法与应用，属于半导体材料及其制备技术领域。The invention relates to a conductive silver paste doped with a silver salt, a preparation method and application thereof, and belongs to the technical field of semiconductor materials and preparation thereof.
背景技术Background technique
导电胶作为电子封装领域传统封装材料—焊料的替代者，其具有很多优点，如：环境友好，无有毒金属，工艺中无需预清洗和焊后清洗；固化温度温和，大大降低了对电子器件的热损伤和内应力，特别适用于热敏性材料和不可焊接的材料；线分辨率高，其200μm以下的线分辨率更适合精细间距制造。导电胶的诸多优点，适应了当今电子器件小型化、轻薄化、集成化的发展趋势，因此其被广泛的应用于IC封装、LED封装、太阳能电池、射频天线等微电子封装领域。As a substitute for solder, the traditional packaging material in the field of electronic packaging, conductive adhesive has many advantages, such as: environmentally friendly, no toxic metal, no pre-cleaning and post-weld cleaning in the process; mild curing temperature, greatly reducing the electronic device Thermal damage and internal stress, especially suitable for heat sensitive materials and non-weldable materials; high line resolution, and line resolution below 200μm is more suitable for fine pitch manufacturing. Many advantages of conductive adhesives have been adapted to the development trend of miniaturization, thinning and integration of electronic devices, so they are widely used in microelectronic packaging such as IC packaging, LED packaging, solar cells, and RF antennas.
导电胶一般由树脂、导电填料和添加剂组成，经固化或干燥后形成具有一定导电、导热、力学等综合性能的胶黏剂。虽然在很多电子领域导电胶已经代替锡铅焊料，但是其还是普遍存在一些缺点，如：体积电阻率偏高，粘接强度不够，储存运输性能较差等。因此，人们为了提高导电胶的导电性能，往往会增加金属填料的含量(65％-90％)，增加金属填料的含量虽然能在一定程度上增加其导电性，但也会因为树脂含量的减少而使导电胶丧失部分机械性能，同时还使得导电胶的粘度增大，粘结强度以及操作性能降低，而且还大大地提高了导电胶的成本。经过长时间的摸索，为获得导电性能优异，粘度适中，操作性能优良，而且低成本的产品，本领域技术人员一般采取如下几种方法：The conductive adhesive is generally composed of a resin, a conductive filler and an additive, and is cured or dried to form an adhesive having a certain conductivity, heat conduction, mechanics and the like. Although conductive glue has replaced tin-lead solder in many electronic fields, it still has some shortcomings, such as high volume resistivity, insufficient bonding strength, and poor storage and transportation performance. Therefore, in order to improve the electrical conductivity of the conductive adhesive, the content of the metal filler is often increased (65%-90%). Although increasing the content of the metal filler can increase its conductivity to some extent, it is also due to the decrease of the resin content. The conductive adhesive loses part of the mechanical properties, and at the same time, the viscosity of the conductive adhesive increases, the bond strength and the handling performance are lowered, and the cost of the conductive adhesive is greatly increased. After a long period of exploration, in order to obtain an excellent electrical conductivity, moderate viscosity, excellent handling performance, and low cost products, the following methods are generally adopted by those skilled in the art:
1、使用固化收缩率高的树脂；在固化过程中，原本相互远离的颗粒会相互靠近，原本相互靠近的颗粒会相互贴近，原本相互贴近的颗粒会相互紧贴，这些均会在一定程度上降低颗粒间的接触电阻或隧道电阻，进而使导电胶体系的总电阻减小，从而获得较低的体积电阻率；1. Use a resin with high cure shrinkage; during the curing process, the particles that are far away from each other will be close to each other, and the particles that are close to each other will be close to each other, and the particles that are close to each other will closely adhere to each other, and these will be to some extent. Reducing the contact resistance or tunnel resistance between the particles, thereby reducing the total resistance of the conductive paste system, thereby obtaining a lower volume resistivity;
2、对金属填料表面改性，如Li等人(Li Y,Moon K S,C P Wong.Electrical Property Improvement of Electrically Conductive Adhesives Through In-situ Replace ment by Short-chain Difunctional Acids[J].IEEE Transactions on Components and  Packaging Technologies,2006,29(1):173-178.)利用己二酸、戊二酸、硅烷偶联剂等溶液对银粉表面进行处理，通过短链酸部分消除或取代了银粉表面的长链酸，使得金属填料之间接触电阻减少，提高了导电性；2. Surface modification of metal fillers, such as Li Y, Moon K S, C P Wong. Electrical Property Improvement of Electrically Conductive Adhesives Through In-situ Replacement by Short-chain Difunctional Acids[J]. On Components and Packaging Technologies, 2006, 29(1): 173-178.) The surface of the silver powder is treated with a solution of adipic acid, glutaric acid, silane coupling agent, etc., and the long chain of the surface of the silver powder is partially eliminated or replaced by the short chain acid. The acid reduces the contact resistance between the metal fillers and improves the conductivity;
3、低熔点金属的添加，有学者研究发现(Kim J M,Yasuda K,Fujimoto K.N ovel Interconnection Method Using Electrically Conductive Paste with Fusible Filler[J].Journal of Electronic Materials,2005,34(5):600-604.Kim H,Kim J,Kim J.Effects of Novel Carboxylic Acid-based Reductants on the Wetting Characteristics o f Anisotropic Conductive Adhesive with Low Melting Point Alloy Filler[J].Microel ectronics Reliability,2010,50(2):258-265.)在导电胶中添加Sn-In等低熔点合金时，由于这些合金具有较低的熔点，在导电胶固化过程中，这些低熔点合金受热后熔化、浸润在银粉周围，与银粉形成一个多元化的冶金结合，从而可以提高导电胶的导电性能；3. The addition of low melting point metals has been studied by scholars (Kim J M, Yasuda K, Fujimoto KN ovel Interconnection Method Using Electrically Conductive Paste with Fusible Filler [J]. Journal of Electronic Materials, 2005, 34(5): 600- 604. Kim H, Kim J, Kim J. Effects of Novel Carboxylic Acid-based Reductants on the Wetting Characteristics o f Anisotropic Conductive Adhesive with Low Melting Point Alloy Filler [J]. Microel ectronics Reliability, 2010, 50(2): 258 -265.) When a low melting point alloy such as Sn-In is added to the conductive paste, since these alloys have a lower melting point, these low melting point alloys are heated and melted and infiltrated around the silver powder during the curing of the conductive paste to form a silver powder. A diversified metallurgical combination that improves the conductivity of the conductive paste;
4、纳米填料的掺杂，研究人员将纳米银线、银纳米颗粒、银纳米片、碳纳米管、石墨烯等其中的一种或几种引入到导电胶中，由于形成新的导电通路或固化过程中纳米导电填料烧结，极大地减少了原导电填料之间的接触电阻，可使用较少量的银粉达到很小的体积电阻率。4. Doping of nano-fillers, researchers introduced one or more of nano-silver wires, silver nanoparticles, silver nano-sheets, carbon nanotubes, graphene, etc. into conductive paste, due to the formation of new conductive pathways or The sintering of the nano-conductive filler during the curing process greatly reduces the contact resistance between the original conductive fillers, and a small amount of silver powder can be used to achieve a small volume resistivity.
因此，针对目前导电银胶存在的电导率相对较低，粘结性不强，成本高等问题，开发出一种电导率相对较高，粘结性较强且低成本的导电银胶已经成为本领域亟需解决的技术问题。Therefore, in view of the fact that the current conductive silver paste has relatively low electrical conductivity, low cohesiveness and high cost, a conductive silver paste having a relatively high conductivity, strong adhesion and low cost has been developed. The technical problems that the field needs to solve.
发明内容Summary of the invention
为了解决上述的缺点和不足，本发明的目的在于提供一种掺杂银盐的导电银胶的制备方法。In order to solve the above disadvantages and disadvantages, an object of the present invention is to provide a method for preparing a conductive silver paste doped with a silver salt.
本发明的目的还在于提供一种由上述掺杂银盐的导电银胶的制备方法制备得到的掺杂银盐的导电银胶。Another object of the present invention is to provide a silver salt-doped conductive silver paste prepared by the above method for preparing a silver salt-doped conductive silver paste.
本发明的目的还在于提供上述掺杂银盐的导电银胶作为半导体电子封装材料的应用。It is also an object of the present invention to provide an application of the above-described silver salt-doped conductive silver paste as a semiconductor electronic packaging material.
为达到上述目的，一方面，本发明提供了一种掺杂银盐的导电银胶，其是由以下原料制备得到的：In order to achieve the above object, in one aspect, the present invention provides a conductive silver paste doped with a silver salt, which is prepared from the following materials:
银盐 0.01～5重量份； Silver salt 0.01 to 5 parts by weight;
微米银粉 50～85重量份；Micron silver powder 50 to 85 parts by weight;
环氧树脂 10～50重量份；Epoxy resin 10 to 50 parts by weight;
固化剂 0.5～60重量份；Curing agent 0.5 to 60 parts by weight;
促进剂 0.05～5重量份；Promoter 0.05 to 5 parts by weight;
偶联剂 0.05～5重量份；Coupling agent 0.05 to 5 parts by weight;
稀释剂 1～10重量份；Diluent 1 to 10 parts by weight;
防沉淀剂 0.05～2重量份。Anti-precipitation agent 0.05 to 2 parts by weight.
根据本发明所述的掺杂银盐的导电银胶，其是通过以下步骤制备得到的：The silver salt-doped conductive silver paste according to the present invention is prepared by the following steps:
(1)将银盐填入环氧树脂中并使其分散均匀，得到基础树脂A；(1) filling the silver salt into the epoxy resin and dispersing it uniformly to obtain the base resin A;
(2)将稀释剂、防沉淀剂、偶联剂、固化剂、促进剂添加到所述基础树脂A中，研磨均匀后，混合脱泡，得到基础树脂B；(2) adding a diluent, an anti-precipitating agent, a coupling agent, a curing agent, an accelerator to the base resin A, after grinding uniformly, mixing and defoaming, to obtain a base resin B;
(3)将微米银粉添加到所述基础树脂B中，研磨均匀后，混合脱泡，得到所述掺杂银盐的导电银胶。(3) Micron silver powder is added to the base resin B, and after grinding uniformly, the mixture is defoamed to obtain the conductive silver paste doped with a silver salt.
根据本发明所述的掺杂银盐的导电银胶，优选地，所述银盐包括硝酸银、醋酸银及卤化银中的一种或几种的组合。In the silver-doped conductive silver paste according to the present invention, preferably, the silver salt comprises one or a combination of silver nitrate, silver acetate, and silver halide.
根据本发明所述的掺杂银盐的导电银胶，在本发明具体实施方式中，所用卤化银可以为氟化银、氯化银、溴化银及碘化银中的一种或几种的组合。According to the silver-doped conductive silver paste of the present invention, in the embodiment of the present invention, the silver halide used may be one or a combination of silver fluoride, silver chloride, silver bromide and silver iodide. .
根据本发明所述的掺杂银盐的导电银胶，优选地，所述微米银粉选自片状、球状及棒状银粉中的一种或几种的组合，该微米银粉的尺寸为1～10μm。The silver salt-doped conductive silver paste according to the present invention, preferably, the micron silver powder is selected from one or a combination of a sheet-like, spherical and rod-shaped silver powder having a size of 1 to 10 μm. .
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。The "size" of irregularly shaped metallic silver powder is defined in the art as the length of the longest portion of the plane.
本发明中涉及的“几种银粉的组合”可以为几种银粉按照任何合适的比例进行的组合，本发明对这几种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，上述几种微米银粉的用量总和需要满足本发明对原料用量的限定。The "combination of several kinds of silver powders" involved in the present invention may be a combination of several kinds of silver powders according to any suitable ratio. The present invention does not require the proportional relationship between the amounts of the silver powders, and those skilled in the art can perform on-site operations. Need to choose the appropriate dosage ratio relationship, however, it should be noted that the sum of the above-mentioned several kinds of micron silver powder needs to meet the limit of the amount of raw materials used in the present invention.
根据本发明所述的掺杂银盐的导电银胶，本发明所用的环氧树脂可以为现有技术中公开的可适用于制备导电银胶的任何一种环氧树脂；优选地，所述环氧树脂包括双酚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、耐高温AG-80/90环氧树脂、TDE-85环氧树脂、脂环族环氧树脂及酚醛环氧树脂中的一种或几种的组合。 According to the silver-doped conductive silver paste of the present invention, the epoxy resin used in the present invention may be any epoxy resin disclosed in the prior art which is applicable to the preparation of conductive silver paste; preferably, the Epoxy resin includes bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, bisphenol F epoxy resin, hydan epoxy resin, high temperature resistant AG-80/90 epoxy resin, TDE-85 ring A combination of one or more of an oxyresin, an alicyclic epoxy resin, and a novolac epoxy resin.
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。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. However, it should be noted that 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.
根据本发明所述的掺杂银盐的导电银胶，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用于制备导电银胶的任何一种脂环族环氧树脂均可以用于本发明；在本发明具体实施方式中，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、环氧-269、环氧-206、环氧-201(阿克苏诺贝尔公司生产)等。According to the silver-doped conductive silver paste of the present invention, the alicyclic epoxy resin used is a conventional product in the art, and any of the alicyclic groups disclosed in the prior art which can be applied to the preparation of the conductive silver paste. Epoxy resins can be used in the present invention; in a specific embodiment of the invention, the cycloaliphatic epoxy resin comprises 3,4-epoxycyclohexenemethyl-3,4-epoxycyclohexenoate , 4,5-epoxycyclohexane-1,2-dicarboxylic acid diglycidyl ester or bis((3,4-epoxycyclohexyl)methyl) adipate, epoxy-269, epoxy- 206, epoxy-201 (produced by AkzoNobel) and the like.
根据本发明所述的掺杂银盐的导电银胶，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用于制备导电银胶的任何一种海因环氧树脂均可以用于本发明。According to the silver-doped conductive silver paste of the present invention, the hydantoin used is a conventional product in the art, and any of the hydantoins disclosed in the prior art which can be applied to the preparation of the conductive silver paste. Resins can be used in the present invention.
根据本发明所述的掺杂银盐的导电银胶，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用于制备导电银胶的任何一种酚醛环氧树脂均可以用于本发明；在本发明具体的实施方式中，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。According to the silver-doped conductive silver paste of 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 applied to the preparation of the conductive silver paste is It can be used in the present invention; in a specific embodiment of the present invention, the phenolic epoxy resin comprises a phenolic epoxy resin of the type EPALOLD-8240 produced by Emerald Company of the United States; and the model of NPPN produced by Taiwan Nanya Plastic Industry Co., Ltd. -631 of phenolic epoxy resin; Dow Chemical (DOW) model DEN431, DEN438 phenolic epoxy resin; Guangzhou Kailuo Chemical Co., Ltd. produced model F-51 phenolic epoxy resin.
根据本发明所述的掺杂银盐的导电银胶，所用双酚F型环氧树脂为本领域使用的常规物质，在本发明具体实施方式中，其包括美国陶氏化学(DOW)生产的型号为DER354的双酚F型环氧树脂。According to the silver-doped conductive silver paste of the present invention, the bisphenol F-type epoxy resin used is a conventional substance used in the art, and in a specific embodiment of the present invention, it comprises a Dow produced by the United States. Model DER354 bisphenol F epoxy resin.
根据本发明所述的掺杂银盐的导电银胶，本发明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，所述固化剂包括咪唑类固化剂、咪唑改性物类固化剂、芳香族胺类固化剂、芳香族胺改性物类固化剂、双氰胺类固化剂、双氰胺衍生物类固化剂、酸酐类固化剂、有机酸酰肼固化剂、三氟化硼-胺络合物固化剂、多胺盐固化剂、微胶囊化固化剂中的一种或几种的组合；According to the silver-doped conductive silver paste of the present invention, the curing agent used in the present invention may be any curing agent disclosed in the prior art which is suitable for the conductive silver paste; preferably, the curing agent includes Imidazole curing agent, imidazole modified curing agent, aromatic amine curing agent, aromatic amine modified curing agent, dicyandiamide curing agent, dicyandiamide derivative curing agent, acid anhydride curing agent a combination of one or more of an organic acid hydrazide curing agent, a boron trifluoride-amine complex curing agent, a polyamine salt curing agent, and a microencapsulated curing agent;
更优选地，所述固化剂为双氰胺类固化剂或双氰胺衍生物类固化剂。More preferably, the curing agent is a dicyandiamide-based curing agent or a dicyandiamide derivative-based curing agent.
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。The "combination of several curing agents" involved in the present invention may be several curing agents in any suitable ratio. The combination of the lines, the present invention does not require the proportional relationship between the amounts of the curing agents, and those skilled in the art can select the appropriate dosage ratio according to the needs of the field operation, but it should be noted that the above several curing agents The sum of the amounts used needs to meet the limits of the amount of raw materials used in the present invention.
本发明所用的咪唑类固化剂为本领域常规的物质，在本发明具体实施方式中，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。The imidazole curing agent used in the present invention is a material conventional in the art. In the specific embodiment of the present invention, the imidazole curing agent includes 2-methylimidazole, 2-phenylimidazole, 2-ethyl-4-methyl Imidazole or 1,2-dimethylimidazole.
本发明所用的咪唑改性物类固化剂为本领域常规的物质，在本发明具体的实施方式中，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、咪唑改性固化剂BMI、PN-23、PN-31、PN-40或PN-50；The imidazole modified type curing agent used in the present invention is a material conventional in the art. In a specific embodiment of the present invention, the imidazole modified substance curing agent comprises a cyanoethyl modified imidazole curing agent, a long alkyl group. Chain modified imidazole curing agent, imidazole modified curing agent BMI, PN-23, PN-31, PN-40 or PN-50;
更具体地，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；More specifically, the cyanoethyl modified imidazole curing agent comprises 1-cyanoethyl-2-ethyl-4-methylimidazole or 1-cyanoethyl-2-phenylimidazole;
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。The long alkyl chain-modified imidazole curing agent includes 2-heptadecylimidazole or 2,4-diamino-6-(2-undecylimidazolyl)-1-ethyltriazine.
其中，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；Wherein, the 2-heptadecylimidazole used is a long alkyl chain-modified imidazole curing agent of the type C17Z produced by Shikoku Chemicals Co., Ltd.;
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；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;
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。The PN-23, PN-31, PN-40, and PN-50 used were all imidazole-modified curing agents produced by Ajinomoto Co., Ltd.
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'-亚甲基二苯胺、对氨基苯酚、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；所述芳香族胺改性物类固化剂包括卤代苯酚、酰化苯酚及磺化苯酚等。The aromatic amine-based curing agent used in the present invention is a conventional one in the art, and the aromatic amine-based curing agent includes 4,4'-methylenediphenylamine, p-aminophenol, 4,4'-diaminodiphenyl. Methane, 4,4'-diaminodiphenyl sulfone, m-phenylenediamine, m-xylylenediamine or diethyltoluenediamine; the aromatic amine modified type curing agent includes halogenated phenol, acylation Phenol and sulfonated phenol.
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；在本发明具体的实施方式中，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。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 A dicyandiamide or benzoquinone-modified dicyandiamide; in a specific 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.
本发明所用的酸酐类固化剂为本领域常规的物质，所述酸酐类固化剂包括邻苯二甲酸酐、四氢邻苯二甲酸酐、偏苯三甲酸酐甘油酯、聚壬二酸酐、桐油酸酐、甲基六氢苯酐。 The acid anhydride type curing agent used in the present invention is a substance conventionally known in the art, and the acid anhydride type curing agent includes phthalic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride glyceride, polysebacic anhydride, and tung oil anhydride. Methyl hexahydrophthalic anhydride.
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、癸二酸二酰肼、间苯二甲酸酰肼或对羟基安息香酸酰肼(POBH)。The organic acid hydrazide-based curing agent used in the present invention is a substance conventionally known in the art, and the organic acid hydrazide-based curing agent includes succinic acid hydrazide, adipic acid dihydrazide, sebacic acid dihydrazide, and isophthalic acid. Formic acid hydrazide or p-hydroxybenzoic acid hydrazide (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。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.
本发明所用的多胺盐固化剂为本领域常规的物质，所述多胺盐固化剂包括羟酸多胺盐等。The polyamine salt curing agent used in the present invention is a substance conventionally known in the art, and the polyamine salt curing agent includes a polyhydroxy acid salt of a hydroxy acid and the like.
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及中南民族大学化学与生命科学学院成功开发的ZHJ-1热控微胶囊型环氧固化剂。The microcapsule curing agent used in the present invention is a conventional curing agent used in the art. In a preferred embodiment of the present invention, 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 and ZHJ-1 thermal control microcapsule epoxy curing agent successfully developed by the School of Chemistry and Life Sciences of Central South University for Nationalities.
根据本发明所述的掺杂银盐的导电银胶，优选地，所述促进剂包括2,4,6-三(二甲氨基甲基)苯酚、2-乙基-4-甲基咪唑、三苯基膦、1-氰乙基-2-乙基-4-甲基咪唑、N,N-二甲基环己胺、N,N-二甲基苄胺、有机脲、四甲基胍、乙酰丙酮的金属盐、过氧化二苯甲酰及芳基异氰酸酯的一种或几种的组合。The silver salt-doped conductive silver paste according to the present invention, preferably, the promoter comprises 2,4,6-tris(dimethylaminomethyl)phenol, 2-ethyl-4-methylimidazole, Triphenylphosphine, 1-cyanoethyl-2-ethyl-4-methylimidazole, N,N-dimethylcyclohexylamine, N,N-dimethylbenzylamine, organic urea, tetramethylguanidine A combination of one or more of a metal salt of acetylacetone, dibenzoyl peroxide and aryl isocyanate.
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。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.
根据本发明所述的掺杂银盐的导电银胶，所用的有机脲促进剂为本领域常规的物质，其具体包括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。The silver-doped conductive silver paste according to the present invention, the organic urea promoter used is a conventional substance in the art, and specifically includes N-p-chlorophenyl-N,N'-dimethylurea, dimethyl The type of imidazole urea, Evonik Degussa produced by UR-200, UR-300 and UR-500, and the model produced by Emerald Performance Materials LLC are OMICURE U- Organic urea of 24M, OMICURE U-35M, OMICURE U-52M and OMICURE U-405M.
根据本发明所述的掺杂银盐的导电银胶，所用的乙酰丙酮的金属盐为本领域常用的产品，在本发明具体实施方式中，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。 According to the silver-doped conductive silver paste of the present invention, the metal salt of acetylacetone used is a product commonly used in the art. In a specific embodiment of the invention, the metal salt of acetylacetone comprises 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.
根据本发明所述的掺杂银盐的导电银胶，优选地，所述偶联剂包括硅烷偶联剂、钛酸酯偶联剂、铝酸酯偶联剂、双金属偶联剂、木质素偶联剂及锡偶联剂中的一种或几种的组合。According to the silver salt-doped conductive silver paste of the present invention, preferably, the coupling agent comprises a silane coupling agent, a titanate coupling agent, an aluminate coupling agent, a bimetallic coupling agent, and wood. A combination of one or more of a coupling agent and a tin coupling agent.
本发明中涉及的“几种偶联剂的组合”可以为几种偶联剂按照任何合适的比例进行的组合，本发明对这几种偶联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，上述几种偶联剂的用量总和需要满足本发明对原料用量的限定。The "combination of several coupling agents" involved in the present invention may be a combination of several coupling agents in any suitable ratio, and the present invention does not require a ratio relationship between the coupling agents. The skilled person can select the appropriate dosage ratio according to the needs of the field operation, but it should be noted that the sum of the above-mentioned several coupling agents needs to meet the limit of the amount of the raw materials of the present invention.
在本发明具体的实施方式中，所述硅烷偶联剂为本领域常规的物质，其包括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、γ-(甲基丙烯酰氧)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-570的偶联剂)及γ-巯丙基三甲氧基硅烷(如南京向前化工有限公司生产的型号为KH-590的偶联剂)；In a specific embodiment of the present invention, the silane coupling agent is a conventional substance in the art, and includes γ-aminopropyltriethoxysilane and γ-aminopropyltrimethoxysilane (such as Nanjing Qianjin Chemical Co., Ltd. Co., Ltd. produces KH-550 coupling agent), γ-(2,3-epoxypropoxy)propyltrimethoxysilane (such as KH-560 produced by Nanjing Qianjin Chemical Co., Ltd.) Coupling agent), γ-(ethylenediamine)propyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, γ-(methacryloyloxy)propyl Trimethoxysilane (such as KH-570 coupling agent produced by Nanjing Forward Chemical Co., Ltd.) and γ-mercaptopropyltrimethoxysilane (such as KH-590 produced by Nanjing Qianjin Chemical Co., Ltd.) Coupling agent);
所用的钛酸酯偶联剂为本领域常规的物质，其包括异丙基三(异硬脂酰基)钛酸酯、异丙基三(十二烷基苯磺酰基)钛酸酯及异丙基三(二辛基焦磷酸酰氧基)钛酸酯TMC-201；The titanate coupling agent used is conventional in the art and includes isopropyl tris(isostearyl) titanate, isopropyl tris(dodecylbenzenesulfonyl) titanate and isopropyl Base three (dioctyl pyrophosphoryloxy) titanate TMC-201;
所用的铝酸酯偶联剂为本领域常规的物质，其包括二硬脂酰氧异丙基铝酸酯或铝酸酯偶联剂F-1(如河南省济源科汇材料有限公司所生产的产品)。The aluminate coupling agent used is a conventional material in the art, which comprises distearyloxyisopropylaluminate or aluminate coupling agent F-1 (such as produced by Henan Jiyuan Kehui Material Co., Ltd.). The product).
所用的双金属偶联剂为本领域常规的物质，其包括锆铝双金属偶联剂TPM(如扬州市立达树脂有限公司所生产的产品)。The bimetallic coupling agent used is a conventional material in the art, and includes a zirconium aluminum bimetallic coupling agent TPM (such as a product produced by Yangzhou Lida Resin Co., Ltd.).
此外，本发明所用的木质素偶联剂及锡偶联剂也均为本领域使用的常规物质，本领域技术人员可以根据现场作业需要选择合适的木质素偶联剂及锡偶联剂，只要能实现偶联的目的即可。In addition, the lignin coupling agent and the tin coupling agent used in the present invention are also conventional materials used in the art, and those skilled in the art can select a suitable lignin coupling agent and a tin coupling agent according to the needs of the field operation, as long as The purpose of coupling can be achieved.
根据本发明所述的掺杂银盐的导电银胶，优选地，所述稀释剂包括正丁基缩水甘油醚、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、C12/14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及间苯二酚二缩水甘油醚中的一种或几种的组合。The silver salt-doped conductive silver paste according to the present invention, preferably, the diluent comprises n-butyl glycidyl ether, 1,4-butanediol diglycidyl ether, trimethylolpropane glycidyl ether , glycerol triglycidyl ether, sterol glycidyl ether, ethylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, allyl glycidyl ether, phenyl glycidyl ether, benzyl glycidyl ether, 2-ethylhexyl glycidyl ether, C12/14 alkyl glycidyl ether, A combination of one or more of diethylene glycol glycidyl ether, p-tert-butyl glycidyl ether, cyclohexanediol diglycidyl ether, and resorcinol diglycidyl ether.
本发明中涉及的“几种稀释剂的组合”可以为几种稀释剂按照任何合适的比例进行的组合，本发明对这几种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，上述几种稀释剂的用量总和需要满足本发明对原料用量的限定。The "combination of several diluents" referred to in the present invention may be a combination of several diluents in any suitable ratio, and the present invention does not require a proportional relationship between the amounts of these diluents, 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 diluents needs to meet the limit of the amount of raw materials used in the present invention.
根据本发明所述的掺杂银盐的导电银胶，优选地，所述防沉淀剂包括气相二氧化硅和/或有机膨润土。According to the silver-doped conductive silver paste of the present invention, preferably, the anti-precipitating agent comprises fumed silica and/or organic bentonite.
当防沉淀剂为气相二氧化硅和有机膨润土的组合时，本发明对这两种物质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，二者的用量总和需要满足本发明对原料用量的限定。When the anti-precipitation agent is a combination of fumed silica and organic bentonite, the present invention does not require a proportional relationship between the two substances, 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 sum of the amounts of the two needs to meet the limit of the amount of raw materials used in the present invention.
另一方面，本发明还提供上述掺杂银盐的导电银胶的制备方法，其包括以下步骤：In another aspect, the present invention also provides a method for preparing the above-mentioned silver salt-doped conductive silver paste, which comprises the following steps:
(1)将银盐填入环氧树脂中并使其分散均匀，得到基础树脂A；(1) filling the silver salt into the epoxy resin and dispersing it uniformly to obtain the base resin A;
(2)将稀释剂、防沉淀剂、偶联剂、固化剂、促进剂添加到所述基础树脂A中，研磨均匀后，混合脱泡，得到基础树脂B；(2) adding a diluent, an anti-precipitating agent, a coupling agent, a curing agent, an accelerator to the base resin A, after grinding uniformly, mixing and defoaming, to obtain a base resin B;
(3)将微米银粉添加到所述基础树脂B中，研磨均匀后，混合脱泡，得到所述掺杂银盐的导电银胶。(3) Micron silver powder is added to the base resin B, and after grinding uniformly, the mixture is defoamed to obtain the conductive silver paste doped with a silver salt.
根据本发明所述的掺杂银盐的导电银胶的制备方法，其中，该掺杂银盐的导电银胶是在室温下进行制备得到的；The method for preparing a silver salt-doped conductive silver paste according to the present invention, wherein the silver salt-doped conductive silver paste is prepared at room temperature;
此外，本发明对步骤(2)中稀释剂、防沉淀剂、偶联剂、固化剂、促进剂这几种物质的加入顺序没有具体要求。In addition, the present invention has no specific requirements for the order of addition of the diluent, the anti-precipitating agent, the coupling agent, the curing agent, and the accelerator in the step (2).
根据本发明所述的掺杂银盐的导电银胶的制备方法，其中，所用原料及各原料用量如下所示：The method for preparing a silver salt-doped conductive silver paste according to the present invention, wherein the raw materials used and the amounts of the raw materials are as follows:
银盐 0.01～5重量份；Silver salt 0.01 to 5 parts by weight;
微米银粉 50～85重量份；Micron silver powder 50 to 85 parts by weight;
环氧树脂 10～50重量份；Epoxy resin 10 to 50 parts by weight;
固化剂 0.5～60重量份；Curing agent 0.5 to 60 parts by weight;
促进剂 0.05～5重量份；Promoter 0.05 to 5 parts by weight;
偶联剂 0.05～5重量份； Coupling agent 0.05 to 5 parts by weight;
稀释剂 1～10重量份；Diluent 1 to 10 parts by weight;
防沉淀剂 0.05～2重量份。Anti-precipitation agent 0.05 to 2 parts by weight.
根据本发明所述的掺杂银盐的导电银胶的制备方法，所述银盐包括硝酸银、醋酸银、卤化银中的一种或几种的组合。According to the method for preparing a silver salt-doped conductive silver paste according to the present invention, the silver salt comprises one or a combination of silver nitrate, silver acetate, silver halide.
根据本发明所述的掺杂银盐的导电银胶的制备方法，所述微米银粉选自片状、球状及棒状银粉中的一种或几种的组合，该微米银粉的尺寸为1～10um。The method for preparing a silver salt-doped conductive silver paste according to the present invention, wherein the micron silver powder is selected from the group consisting of one or a combination of a sheet-shaped, spherical and rod-shaped silver powder having a size of 1 to 10 μm. .
根据本发明所述的掺杂银盐的导电银胶的制备方法，所述环氧树脂包括双酚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、耐高温AG-80/90环氧树脂、TDE-85环氧树脂、脂环族环氧树脂、酚醛环氧树脂中的一种或几种的组合。A method for preparing a silver salt-doped conductive silver paste according to the present invention, the epoxy resin comprising a bisphenol A type epoxy resin, a hydrogenated bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a sea A combination of one or more of epoxy resin, high temperature resistant AG-80/90 epoxy resin, TDE-85 epoxy resin, alicyclic epoxy resin, and novolac epoxy resin.
根据本发明所述的掺杂银盐的导电银胶的制备方法，所述固化剂包括咪唑类固化剂、咪唑改性物类固化剂、芳香族胺类固化剂、芳香族胺改性物类固化剂、双氰胺类固化剂、双氰胺衍生物类固化剂、酸酐类固化剂、有机酸酰肼固化剂、三氟化硼-胺络合物固化剂、多胺盐固化剂、微胶囊化固化剂中的一种或几种的组合。According to the method for preparing a silver salt-doped conductive silver paste according to the present invention, the curing agent includes an imidazole curing agent, an imidazole modified curing agent, an aromatic amine curing agent, and an aromatic amine modified product. Curing agent, dicyandiamide curing agent, dicyandiamide derivative curing agent, acid anhydride curing agent, organic acid hydrazide curing agent, boron trifluoride-amine complex curing agent, polyamine salt curing agent, micro One or a combination of several of the encapsulated curing agents.
根据本发明所述的掺杂银盐的导电银胶的制备方法，所述促进剂包括2,4,6-三(二甲氨基甲基)苯酚、2-乙基-4-甲基咪唑、三苯基膦、1-氰乙基-2-乙基-4-甲基咪唑、N,N-二甲环己胺、N,N-二甲基苄胺、有机脲、四甲基胍、乙酰丙酮的金属盐、过氧化二苯甲酰及芳基异氰酸酯中的一种或几种的组合。The method for preparing a silver salt-doped conductive silver paste according to the present invention, wherein the promoter comprises 2,4,6-tris(dimethylaminomethyl)phenol, 2-ethyl-4-methylimidazole, Triphenylphosphine, 1-cyanoethyl-2-ethyl-4-methylimidazole, N,N-dimethylcyclohexylamine, N,N-dimethylbenzylamine, organic urea, tetramethylguanidine, A combination of one or more of a metal salt of acetylacetone, dibenzoyl peroxide, and aryl isocyanate.
根据本发明所述的掺杂银盐的导电银胶的制备方法，所述偶联剂包括硅烷偶联剂、钛酸酯偶联剂、铝酸酯偶联剂、双金属偶联剂、木质素偶联剂及锡偶联剂中的一种或几种的组合。The method for preparing a silver salt-doped conductive silver paste according to the present invention, the coupling agent comprises a silane coupling agent, a titanate coupling agent, an aluminate coupling agent, a bimetallic coupling agent, and a wood A combination of one or more of a coupling agent and a tin coupling agent.
根据本发明所述的掺杂银盐的导电银胶的制备方法，所述稀释剂包括正丁基缩水甘油醚、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、C12/14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及间苯二酚二缩水甘油醚中的一种或几种的组合。A method for preparing a silver salt-doped conductive silver paste according to the present invention, the diluent comprising n-butyl glycidyl ether, 1,4-butanediol diglycidyl ether, trimethylolpropane glycidyl ether , glycerol triglycidyl ether, sterol glycidyl ether, ethylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, allyl glycidyl ether, phenyl glycidyl ether, benzyl glycidyl ether, 2-ethylhexyl glycidyl ether, C12/14 alkyl glycidyl ether, diethylene glycol glycidyl ether, p-tert-butyl glycidyl ether, cyclohexanediol diglycidyl ether, and resorcinol diglycidyl One or a combination of ethers.
根据本发明所述的掺杂银盐的导电银胶的制备方法，所述防沉淀剂包括气相二氧化硅和/或有机膨润土。 According to the method for preparing a silver salt-doped conductive silver paste according to the present invention, the anti-precipitation agent comprises fumed silica and/or organic bentonite.
根据本发明所述的掺杂银盐的导电银胶的制备方法，其中，步骤(1)中使银盐在环氧树脂中分散均匀可以通过搅拌研磨来实现，进而得到组分均一的基础树脂A。The method for preparing a silver salt-doped conductive silver paste according to the present invention, wherein the uniform dispersion of the silver salt in the epoxy resin in the step (1) can be achieved by stirring and grinding, thereby obtaining a base resin having uniform composition. A.
根据本发明所述的掺杂银盐的导电银胶的制备方法，其中，步骤(2)中所述的研磨均匀可以通过三辊研磨机来实现，再经混合脱泡，得到组分均一的基础树脂B。The method for preparing a silver salt-doped conductive silver paste according to the present invention, wherein the grinding uniformly described in the step (2) can be achieved by a three-roll mill, and then mixed and defoamed to obtain a uniform composition. Base resin B.
根据本发明所述的掺杂银盐的导电银胶的制备方法，其中，步骤(3)中所述研磨均匀可以通过三辊研磨机来实现，再经混合脱泡，得到膏状的掺杂银盐的导电银胶。The method for preparing a silver salt-doped conductive silver paste according to the present invention, wherein the polishing in the step (3) can be uniformly performed by a three-roll mill, and then mixed and defoamed to obtain a paste-like doping. Conductive silver paste of silver salt.
又一方面，本发明还提供了上述掺杂银盐的导电银胶作为半导体电子封装材料的应用。In still another aspect, the present invention also provides the use of the above-mentioned silver salt-doped conductive silver paste as a semiconductor electronic packaging material.
本发明的制备方法将银盐以掺杂的方式引入到导电银胶配方中，在保证导电银胶导电性能的前提下，可以降低银粉使用量15％～20％；在相同银粉添加量时，导电银胶的电导率大大的提升，而且该导电银胶具有良好的剪切强度和耐老化性能；另，该方法简单易行，所用原料价格较低，降低了导电银胶生产的成本，所制备得到的掺杂银盐的导电银胶可广泛应用于太阳能电池、IC和LED封装等领域。The preparation method of the invention introduces the silver salt into the conductive silver glue formulation in a doping manner, and can reduce the use amount of the silver powder by 15%-20% under the premise of ensuring the conductive property of the conductive silver glue; when the same silver powder is added, The conductivity of the conductive silver glue is greatly improved, and the conductive silver glue has good shear strength and aging resistance; in addition, the method is simple and easy, the raw material used is lower in price, and the cost of the conductive silver glue is reduced. The prepared silver salt-doped conductive silver paste can be widely used in the fields of solar cells, ICs, and LED packages.
此外，本发明将银盐以掺杂的方式引入到导电银胶配方中，引入的少量银盐可以极大地提高导电胶的电导率，降低导电胶的渗流阈值，大大减少了银粉的使用量，降低了成本，达到或者超过现有技术中部分银纳米线，银纳米颗粒、石墨烯等纳米填料的效果(现有技术中添加银纳米线，银纳米颗粒、石墨烯等纳米填料的导电银胶的体积电阻率一般都在10-5级别，与本发明制备得到的掺杂银盐的导电银胶相近，但是其粘结强度没有达到20MPa，明显低于本发明该掺杂银盐的导电银胶的粘结强度，最高可达25MPa)，而且由于本发明所掺杂的银盐不是纳米级，进而本发明制备得到的掺杂银盐的导电银胶不存在纳米填料易团聚、价格昂贵等缺点；所以本发明的制备方法操作方便，实用，对于提高导电银胶的综合性能，降低生产成本具有很大的意义。In addition, the present invention introduces a silver salt into the conductive silver paste formulation in a doped manner, and the introduced small amount of silver salt can greatly improve the electrical conductivity of the conductive adhesive, reduce the percolation threshold of the conductive adhesive, and greatly reduce the amount of silver powder used. Reduce the cost, meet or exceed the effect of some silver nanowires, silver nanoparticles, graphene and other nano-fillers in the prior art (the prior art adds silver nanowires, silver nanoparticles, graphene and other nano-filled conductive silver paste The volume resistivity is generally in the range of 10 -5 , which is similar to the silver-doped conductive silver paste prepared by the present invention, but the bonding strength thereof is not up to 20 MPa, which is significantly lower than the conductive silver doped with the silver salt of the present invention. The bonding strength of the glue can be up to 25 MPa), and since the silver salt doped by the present invention is not nano-scale, the silver-doped conductive silver paste prepared by the invention does not have the nano-filler easy to agglomerate and is expensive. Disadvantages; therefore, the preparation method of the invention is convenient and practical, and has great significance for improving the comprehensive performance of the conductive silver paste and reducing the production cost.
具体实施方式detailed description
为了对本发明的技术特征、目的和有益效果有更加清楚的理解，以下将通过具体的实施例详细地说明本发明的实施过程和产生的有益效果，旨在帮助阅读者更好地理解本发明的实质和特点，但是不作为对本案可实施范围的限定。The embodiments of the present invention and the beneficial effects thereof will be described in detail below by way of specific embodiments, which are intended to provide a better understanding of the present invention. Substance and characteristics, but not as a limitation on the scope of implementation of this case.
实施例1Example 1
本实施例提供了一种掺杂银盐的导电银胶，是由以下原料制备得到的：This embodiment provides a conductive silver paste doped with a silver salt, which is prepared from the following materials:
银盐 (硝酸银) 0.6重量份； Silver salt (silver nitrate) 0.6 parts by weight;
微米银粉 (混合片状棒状银粉，平均粒径5微米) 80重量份；Micron silver powder (mixed sheet-like silver powder, average particle diameter 5 microns) 80 parts by weight;
环氧树脂 (壳牌双酚A型环氧树脂828E) 17重量份；Epoxy resin (Shell bisphenol A type epoxy resin 828E) 17 parts by weight;
固化剂 (双氰胺) 1重量份；Curing agent (dicyandiamide) 1 part by weight;
促进剂 (1-氰乙基-2-乙基-4-甲基咪唑) 0.1重量份；Promoter (1-cyanoethyl-2-ethyl-4-methylimidazole) 0.1 part by weight;
偶联剂 (KH-560) 0.1重量份；Coupling agent (KH-560) 0.1 parts by weight;
稀释剂 (1,4-丁二醇二缩水甘油醚) 1.15重量份；Diluent (1,4-butanediol diglycidyl ether) 1.15 parts by weight;
防沉淀剂 (气相二氧化硅) 0.05重量份；Anti-precipitation agent (fumed silica) 0.05 parts by weight;
上述掺杂银盐的导电银胶的制备方法包括以下步骤：The preparation method of the above silver salt-doped conductive silver paste comprises the following steps:
(1)将硝酸银按照所述比例填入环氧树脂中，搅拌研磨，使得银盐充分的分散，制成组分均一的基础树脂A；(1) The silver nitrate is filled into the epoxy resin according to the ratio, stirred and ground, so that the silver salt is sufficiently dispersed to form a base resin A having a uniform composition;
(2)将稀释剂、防沉淀剂、偶联剂、固化剂、促进剂按所述比例添加到基础树脂A中，混合后用三辊研磨机研磨均匀，混合脱泡，制成组分均一的基础树脂B；(2) adding a diluent, an anti-precipitating agent, a coupling agent, a curing agent, and a promoter to the base resin A in the above ratio, mixing and then uniformly grinding with a three-roll mill, mixing and defoaming to prepare a uniform composition. Base resin B;
(3)将微米银粉按所述比例添加到基础树脂B中，混合均匀后用三辊研磨机研磨，混合脱泡，制成膏状的成品掺杂银盐的导电银胶。(3) The micron silver powder is added to the base resin B in the above ratio, mixed uniformly, and then ground by a three-roll mill, and mixed and defoamed to prepare a paste-like conductive silver paste-doped conductive silver paste.
实施例2Example 2
本实施例提供了一种掺杂银盐的导电银胶，是由以下原料制备得到的：This embodiment provides a conductive silver paste doped with a silver salt, which is prepared from the following materials:
银盐 (硝酸银) 0.6重量份；Silver salt (silver nitrate) 0.6 parts by weight;
微米银粉 (混合片状棒状银粉，平均粒径5微米) 70重量份；Micron silver powder (mixed sheet-like silver powder, average particle diameter 5 μm) 70 parts by weight;
环氧树脂 (壳牌双酚A型环氧树脂828E) 25.0重量份；Epoxy resin (Shell bisphenol A type epoxy resin 828E) 25.0 parts by weight;
固化剂 (双氰胺) 1.4重量份；Curing agent (dicyandiamide) 1.4 parts by weight;
促进剂 (1-氰乙基-2-乙基-4-甲基咪唑) 0.15重量份；Promoter (1-cyanoethyl-2-ethyl-4-methylimidazole) 0.15 parts by weight;
偶联剂 (KH-560) 0.15重量份；Coupling agent (KH-560) 0.15 parts by weight;
稀释剂 (1,4-丁二醇二缩水甘油醚) 2.63重量份；Diluent (1,4-butanediol diglycidyl ether) 2.63 parts by weight;
防沉淀剂 (气相二氧化硅) 0.075重量份；Anti-precipitation agent (fumed silica) 0.075 parts by weight;
上述掺杂银盐的导电银胶的制备方法包括以下步骤：The preparation method of the above silver salt-doped conductive silver paste comprises the following steps:
(1)将硝酸银按照所述比例填入环氧树脂中，搅拌研磨，使得银盐充分的分散，制成组分均一的基础树脂A；(1) The silver nitrate is filled into the epoxy resin according to the ratio, stirred and ground, so that the silver salt is sufficiently dispersed to form a base resin A having a uniform composition;
(2)将稀释剂、防沉淀剂、偶联剂、固化剂、促进剂按所述比例添加到基础树脂A中，混合后用三辊研磨机研磨均匀，混合脱泡，制成组分均一的基础树脂B； (2) adding a diluent, an anti-precipitating agent, a coupling agent, a curing agent, and a promoter to the base resin A in the above ratio, mixing and then uniformly grinding with a three-roll mill, mixing and defoaming to prepare a uniform composition. Base resin B;
(3)将银粉按所述比例添加到基础树脂B中，混合均匀后用三辊研磨机研磨，混合脱泡，制成膏状的成品掺杂银盐的导电银胶。(3) The silver powder is added to the base resin B in the above ratio, uniformly mixed, and then ground by a three-roll mill, and mixed and defoamed to form a paste-like conductive silver paste-doped conductive silver paste.
实施例3Example 3
本实施例提供了一种掺杂银盐的导电银胶，是由以下原料制备得到的：This embodiment provides a conductive silver paste doped with a silver salt, which is prepared from the following materials:
银盐 (硝酸银) 0.6重量份；Silver salt (silver nitrate) 0.6 parts by weight;
微米银粉 (混合片状棒状银粉，平均粒径5微米) 60重量份；Micron silver powder (mixed sheet-like silver powder, average particle diameter 5 microns) 60 parts by weight;
环氧树脂 (壳牌双酚A型环氧树脂828E) 34重量份；Epoxy resin (Shell bisphenol A type epoxy resin 828E) 34 parts by weight;
固化剂 (双氰胺) 2重量份；Curing agent (dicyandiamide) 2 parts by weight;
促进剂 (1-氰乙基-2-乙基-4-甲基咪唑) 0.2重量份；Promoter (1-cyanoethyl-2-ethyl-4-methylimidazole) 0.2 parts by weight;
偶联剂 (KH-560) 0.2重量份；Coupling agent (KH-560) 0.2 parts by weight;
稀释剂 (1,4-丁二醇二缩水甘油醚) 2.9重量份；Diluent (1,4-butanediol diglycidyl ether) 2.9 parts by weight;
防沉淀剂 (气相二氧化硅) 0.1重量份；Anti-precipitation agent (fumed silica) 0.1 part by weight;
上述掺杂银盐的导电银胶的制备方法包括以下步骤：The preparation method of the above silver salt-doped conductive silver paste comprises the following steps:
(1)将硝酸银按照所述比例填入环氧树脂中，搅拌研磨，使得银盐充分的分散，制成组分均一的基础树脂A；(1) The silver nitrate is filled into the epoxy resin according to the ratio, stirred and ground, so that the silver salt is sufficiently dispersed to form a base resin A having a uniform composition;
(2)将稀释剂、防沉淀剂、偶联剂、固化剂、促进剂按所述比例添加到基础树脂A中，混合后用三辊研磨机研磨均匀，混合脱泡，制成组分均一的基础树脂B；(2) adding a diluent, an anti-precipitating agent, a coupling agent, a curing agent, and a promoter to the base resin A in the above ratio, mixing and then uniformly grinding with a three-roll mill, mixing and defoaming to prepare a uniform composition. Base resin B;
(3)将银粉按所述比例添加到基础树脂B中，混合均匀后用三辊研磨机研磨，混合脱泡，制成膏状的成品掺杂银盐的导电银胶。(3) The silver powder is added to the base resin B in the above ratio, uniformly mixed, and then ground by a three-roll mill, and mixed and defoamed to form a paste-like conductive silver paste-doped conductive silver paste.
实施例4Example 4
本实施例提供了一种掺杂银盐的导电银胶，是由以下原料制备得到的：This embodiment provides a conductive silver paste doped with a silver salt, which is prepared from the following materials:
银盐 (溴化银) 0.6重量份；Silver salt (silver bromide) 0.6 parts by weight;
微米银粉 (混合片状棒状银粉，平均粒径5微米) 80重量份；Micron silver powder (mixed sheet-like silver powder, average particle diameter 5 microns) 80 parts by weight;
环氧树脂 (壳牌双酚A型环氧树脂828E) 17重量份；Epoxy resin (Shell bisphenol A type epoxy resin 828E) 17 parts by weight;
固化剂 (双氰胺) 1重量份；Curing agent (dicyandiamide) 1 part by weight;
促进剂 (1-氰乙基-2-乙基-4-甲基咪唑) 0.1重量份；Promoter (1-cyanoethyl-2-ethyl-4-methylimidazole) 0.1 part by weight;
偶联剂 (KH-560) 0.1重量份；Coupling agent (KH-560) 0.1 parts by weight;
稀释剂 (1,4-丁二醇二缩水甘油醚) 1.15重量份；Diluent (1,4-butanediol diglycidyl ether) 1.15 parts by weight;
防沉淀剂 (气相二氧化硅) 0.05重量份； Anti-precipitation agent (fumed silica) 0.05 parts by weight;
上述掺杂银盐的导电银胶的制备方法包括以下步骤：The preparation method of the above silver salt-doped conductive silver paste comprises the following steps:
(1)将溴化银按照所述比例填入环氧树脂中，搅拌研磨，使得银盐充分的分散，制成组分均一的基础树脂A；(1) The silver bromide is filled into the epoxy resin according to the ratio, stirred and ground, so that the silver salt is sufficiently dispersed to form a base resin A having a uniform composition;
(2)将稀释剂、防沉淀剂、偶联剂、固化剂、促进剂按所述比例添加到基础树脂A中，混合后用三辊研磨机研磨均匀，混合脱泡，制成组分均一的基础树脂B；(2) adding a diluent, an anti-precipitating agent, a coupling agent, a curing agent, and a promoter to the base resin A in the above ratio, mixing and then uniformly grinding with a three-roll mill, mixing and defoaming to prepare a uniform composition. Base resin B;
(3)将银粉按所述比例添加到基础树脂B中，混合均匀后用三辊研磨机研磨，混合脱泡，制成膏状的成品掺杂银盐的导电银胶。(3) The silver powder is added to the base resin B in the above ratio, uniformly mixed, and then ground by a three-roll mill, and mixed and defoamed to form a paste-like conductive silver paste-doped conductive silver paste.
实施例5Example 5
本实施例提供了一种掺杂银盐的导电银胶，是由以下原料制备得到的：This embodiment provides a conductive silver paste doped with a silver salt, which is prepared from the following materials:
银盐 (醋酸银) 0.6重量份；Silver salt (silver acetate) 0.6 parts by weight;
微米银粉 (混合片状棒状银粉，平均粒径5微米) 80重量份；Micron silver powder (mixed sheet-like silver powder, average particle diameter 5 microns) 80 parts by weight;
环氧树脂 (壳牌双酚A型环氧树脂828E) 17重量份；Epoxy resin (Shell bisphenol A type epoxy resin 828E) 17 parts by weight;
固化剂 (双氰胺) 1重量份；Curing agent (dicyandiamide) 1 part by weight;
促进剂 (1-氰乙基-2-乙基-4-甲基咪唑) 0.1重量份；Promoter (1-cyanoethyl-2-ethyl-4-methylimidazole) 0.1 part by weight;
偶联剂 (KH-560) 0.1重量份；Coupling agent (KH-560) 0.1 parts by weight;
稀释剂 (1,4-丁二醇二缩水甘油醚) 1.15重量份；Diluent (1,4-butanediol diglycidyl ether) 1.15 parts by weight;
防沉淀剂 (气相二氧化硅) 0.05重量份；Anti-precipitation agent (fumed silica) 0.05 parts by weight;
上述掺杂银盐的导电银胶的制备方法包括以下步骤：The preparation method of the above silver salt-doped conductive silver paste comprises the following steps:
(1)将醋酸银按照所述比例填入环氧树脂中，搅拌研磨，使得银盐充分的分散，制成组分均一的基础树脂A；(1) the silver acetate is filled into the epoxy resin according to the ratio, stirred and ground, so that the silver salt is sufficiently dispersed to form a base resin A having a uniform composition;
(2)将稀释剂、防沉淀剂、偶联剂、固化剂、促进剂按所述比例添加到基础树脂A中，混合后用三辊研磨机研磨均匀，混合脱泡，制成组分均一的基础树脂B；(2) adding a diluent, an anti-precipitating agent, a coupling agent, a curing agent, and a promoter to the base resin A in the above ratio, mixing and then uniformly grinding with a three-roll mill, mixing and defoaming to prepare a uniform composition. Base resin B;
(3)将银粉按所述比例添加到基础树脂B中，混合均匀后用三辊研磨机研磨，混合脱泡，制成膏状的成品掺杂银盐的导电银胶。(3) The silver powder is added to the base resin B in the above ratio, uniformly mixed, and then ground by a three-roll mill, and mixed and defoamed to form a paste-like conductive silver paste-doped conductive silver paste.
实施例6(对比例1)Example 6 (Comparative Example 1)
本实施例提供了一种导电银胶，是由以下原料制备得到的：This embodiment provides a conductive silver paste which is prepared from the following materials:
微米银粉 (混合片状棒状银粉，平均粒径5微米) 80重量份；Micron silver powder (mixed sheet-like silver powder, average particle diameter 5 microns) 80 parts by weight;
环氧树脂 (壳牌双酚A环氧树脂828E) 17.6重量份；Epoxy resin (Shell bisphenol A epoxy resin 828E) 17.6 parts by weight;
固化剂 (双氰胺) 1重量份； Curing agent (dicyandiamide) 1 part by weight;
促进剂 (1-氰乙基-2-乙基-4-甲基咪唑) 0.1重量份；Promoter (1-cyanoethyl-2-ethyl-4-methylimidazole) 0.1 part by weight;
偶联剂 (KH-560) 0.1重量份；Coupling agent (KH-560) 0.1 parts by weight;
稀释剂 (1,4-丁二醇二缩水甘油醚) 1.15重量份；Diluent (1,4-butanediol diglycidyl ether) 1.15 parts by weight;
防沉淀剂 (气相二氧化硅) 0.05重量份；Anti-precipitation agent (fumed silica) 0.05 parts by weight;
上述掺杂银盐的导电银胶的制备方法包括以下步骤：The preparation method of the above silver salt-doped conductive silver paste comprises the following steps:
(1)将稀释剂、防沉淀剂、偶联剂、固化剂、促进剂按所述比例添加到环氧树脂中，混合后用三辊研磨机研磨均匀，混合脱泡，制成组分均一的基础树脂1；(1) adding diluent, anti-precipitating agent, coupling agent, curing agent and accelerator to the epoxy resin in the above ratio, mixing and grinding uniformly with a three-roll mill, mixing and defoaming to prepare a uniform composition Base resin 1;
(2)将微米银粉按所述比例添加到基础树脂1中，混合均匀后用三辊研磨机研磨，混合脱泡，制成膏状的成品导电银胶。(2) The micron silver powder is added to the base resin 1 in the above ratio, mixed uniformly, and then ground by a three-roll mill, and mixed and defoamed to obtain a paste-like finished conductive silver paste.
实施例7Example 7
本实施例提供了一种掺杂银盐的导电银胶，是由以下原料制备得到的：This embodiment provides a conductive silver paste doped with a silver salt, which is prepared from the following materials:
银盐 (硝酸银) 0.6重量份；Silver salt (silver nitrate) 0.6 parts by weight;
微米银粉 (混合片状棒状银粉，平均粒径5微米) 80重量份；Micron silver powder (mixed sheet-like silver powder, average particle diameter 5 microns) 80 parts by weight;
环氧树脂 (TDE-85) 14重量份；Epoxy resin (TDE-85) 14 parts by weight;
固化剂 (4,4'-亚甲基二苯胺) 4.0重量份；Curing agent (4,4'-methylenediphenylamine) 4.0 parts by weight;
促进剂 (N,N-二甲环己胺) 0.1重量份；Promoter (N,N-dimethylcyclohexylamine) 0.1 parts by weight;
偶联剂 (KH-550) 0.1重量份；Coupling agent (KH-550) 0.1 parts by weight;
稀释剂 (丙三醇三缩水甘油醚) 1.15重量份；Diluent (glycerol triglycidyl ether) 1.15 parts by weight;
防沉淀剂 (气相二氧化硅) 0.05重量份；Anti-precipitation agent (fumed silica) 0.05 parts by weight;
上述掺杂银盐的导电银胶的制备方法包括以下步骤：The preparation method of the above silver salt-doped conductive silver paste comprises the following steps:
(1)将硝酸银按照所述比例填入环氧树脂中，搅拌研磨，使得银盐充分的分散，制成组分均一的基础树脂A；(1) The silver nitrate is filled into the epoxy resin according to the ratio, stirred and ground, so that the silver salt is sufficiently dispersed to form a base resin A having a uniform composition;
(2)将稀释剂、防沉淀剂、偶联剂、固化剂、促进剂按所述比例添加到基础树脂A中，混合后用三辊研磨机研磨均匀，混合脱泡，制成组分均一的基础树脂B；(2) adding a diluent, an anti-precipitating agent, a coupling agent, a curing agent, and a promoter to the base resin A in the above ratio, mixing and then uniformly grinding with a three-roll mill, mixing and defoaming to prepare a uniform composition. Base resin B;
(3)将银粉按所述比例添加到基础树脂B中，混合均匀后用三辊研磨机研磨，混合脱泡，制成膏状的成品掺杂银盐的导电银胶。(3) The silver powder is added to the base resin B in the above ratio, uniformly mixed, and then ground by a three-roll mill, and mixed and defoamed to form a paste-like conductive silver paste-doped conductive silver paste.
实施例8Example 8
本实施例提供了一种掺杂银盐的导电银胶，是由以下原料制备得到的：This embodiment provides a conductive silver paste doped with a silver salt, which is prepared from the following materials:
银盐 (溴化银) 0.6重量份； Silver salt (silver bromide) 0.6 parts by weight;
微米银粉 (混合片状棒状银粉，平均粒径5微米) 80重量份；Micron silver powder (mixed sheet-like silver powder, average particle diameter 5 microns) 80 parts by weight;
环氧树脂 (TDE-85) 14重量份；Epoxy resin (TDE-85) 14 parts by weight;
固化剂 (4,4'-亚甲基二苯胺) 4.0重量份；Curing agent (4,4'-methylenediphenylamine) 4.0 parts by weight;
促进剂 (N,N-二甲环己胺) 0.1重量份；Promoter (N,N-dimethylcyclohexylamine) 0.1 parts by weight;
偶联剂 (KH-550) 0.1重量份；Coupling agent (KH-550) 0.1 parts by weight;
稀释剂 (丙三醇三缩水甘油醚) 1.15重量份；Diluent (glycerol triglycidyl ether) 1.15 parts by weight;
防沉淀剂 (气相二氧化硅) 0.05重量份；Anti-precipitation agent (fumed silica) 0.05 parts by weight;
上述掺杂银盐的导电银胶的制备方法包括以下步骤：The preparation method of the above silver salt-doped conductive silver paste comprises the following steps:
(1)将溴化银按照所述比例填入环氧树脂中，搅拌研磨，使得银盐充分的分散，制成组分均一的基础树脂A；(1) The silver bromide is filled into the epoxy resin according to the ratio, stirred and ground, so that the silver salt is sufficiently dispersed to form a base resin A having a uniform composition;
(2)将稀释剂、防沉淀剂、偶联剂、固化剂、促进剂按所述比例添加到基础树脂A中，混合后用三辊研磨机研磨均匀，混合脱泡，制成组分均一的基础树脂B；(2) adding a diluent, an anti-precipitating agent, a coupling agent, a curing agent, and a promoter to the base resin A in the above ratio, mixing and then uniformly grinding with a three-roll mill, mixing and defoaming to prepare a uniform composition. Base resin B;
(3)将银粉按所述比例添加到基础树脂B中，混合均匀后用三辊研磨机研磨，混合脱泡，制成膏状的成品掺杂银盐的导电银胶。(3) The silver powder is added to the base resin B in the above ratio, uniformly mixed, and then ground by a three-roll mill, and mixed and defoamed to form a paste-like conductive silver paste-doped conductive silver paste.
实施例9Example 9
本实施例提供了一种掺杂银盐的导电银胶，是由以下原料制备得到的：This embodiment provides a conductive silver paste doped with a silver salt, which is prepared from the following materials:
银盐 (醋酸银) 0.6重量份；Silver salt (silver acetate) 0.6 parts by weight;
微米银粉 (混合片状棒状银粉，平均粒径5微米) 80重量份；Micron silver powder (mixed sheet-like silver powder, average particle diameter 5 microns) 80 parts by weight;
环氧树脂 (TDE-85) 14重量份；Epoxy resin (TDE-85) 14 parts by weight;
固化剂 (4,4'-亚甲基二苯胺) 4.0重量份；Curing agent (4,4'-methylenediphenylamine) 4.0 parts by weight;
促进剂 (N,N-二甲环己胺) 0.1重量份；Promoter (N,N-dimethylcyclohexylamine) 0.1 parts by weight;
偶联剂 (KH-550) 0.1重量份；Coupling agent (KH-550) 0.1 parts by weight;
稀释剂 (丙三醇三缩水甘油醚) 1.15重量份；Diluent (glycerol triglycidyl ether) 1.15 parts by weight;
防沉淀剂 (气相二氧化硅) 0.05重量份；Anti-precipitation agent (fumed silica) 0.05 parts by weight;
上述掺杂银盐的导电银胶的制备方法包括以下步骤：The preparation method of the above silver salt-doped conductive silver paste comprises the following steps:
(1)将醋酸银按照所述比例填入环氧树脂中，搅拌研磨，使得银盐充分的分散，制成组分均一的基础树脂A；(1) the silver acetate is filled into the epoxy resin according to the ratio, stirred and ground, so that the silver salt is sufficiently dispersed to form a base resin A having a uniform composition;
(2)将稀释剂、防沉淀剂、偶联剂、固化剂、促进剂按所述比例添加到基础树脂A中，混合后用三辊研磨机研磨均匀，混合脱泡，制成组分均一的基础树脂B； (2) adding a diluent, an anti-precipitating agent, a coupling agent, a curing agent, and a promoter to the base resin A in the above ratio, mixing and then uniformly grinding with a three-roll mill, mixing and defoaming to prepare a uniform composition. Base resin B;
(3)将银粉按所述比例添加到基础树脂B中，混合均匀后用三辊研磨机研磨，混合脱泡，制成膏状的成品掺杂银盐的导电银胶。(3) The silver powder is added to the base resin B in the above ratio, uniformly mixed, and then ground by a three-roll mill, and mixed and defoamed to form a paste-like conductive silver paste-doped conductive silver paste.
实施例10(对比例2)Example 10 (Comparative Example 2)
本实施例提供了一种导电银胶，是由以下原料制备得到的：This embodiment provides a conductive silver paste which is prepared from the following materials:
微米银粉 (混合片状棒状银粉，平均粒径5微米) 80重量份；Micron silver powder (mixed sheet-like silver powder, average particle diameter 5 microns) 80 parts by weight;
环氧树脂 (TDE-85) 14重量份；Epoxy resin (TDE-85) 14 parts by weight;
固化剂 (4,4'-亚甲基二苯胺) 4.0重量份；Curing agent (4,4'-methylenediphenylamine) 4.0 parts by weight;
促进剂 (N,N-二甲环己胺) 0.1重量份；Promoter (N,N-dimethylcyclohexylamine) 0.1 parts by weight;
偶联剂 (KH-590) 0.1重量份；Coupling agent (KH-590) 0.1 parts by weight;
稀释剂 (2-乙基己基缩水甘油醚) 1.15重量份；Diluent (2-ethylhexyl glycidyl ether) 1.15 parts by weight;
防沉淀剂 (气相二氧化硅) 0.05重量份；Anti-precipitation agent (fumed silica) 0.05 parts by weight;
上述掺杂银盐的导电银胶的制备方法包括以下步骤：The preparation method of the above silver salt-doped conductive silver paste comprises the following steps:
(1)将稀释剂、防沉淀剂、偶联剂、固化剂、促进剂按所述比例添加到环氧树脂中，混合后用三辊研磨机研磨均匀，混合脱泡，制成组分均一的基础树脂1；(1) adding diluent, anti-precipitating agent, coupling agent, curing agent and accelerator to the epoxy resin in the above ratio, mixing and grinding uniformly with a three-roll mill, mixing and defoaming to prepare a uniform composition Base resin 1;
(2)将微米银粉按所述比例添加到基础树脂1中，混合均匀后用三辊研磨机研磨，混合脱泡，制成膏状的成品导电银胶。(2) The micron silver powder is added to the base resin 1 in the above ratio, mixed uniformly, and then ground by a three-roll mill, and mixed and defoamed to obtain a paste-like finished conductive silver paste.
实施例11Example 11
本实施例提供了一种掺杂银盐的导电银胶，是由以下原料制备得到的：This embodiment provides a conductive silver paste doped with a silver salt, which is prepared from the following materials:
银盐 (硝酸银)0.6重量份；Silver salt (silver nitrate) 0.6 parts by weight;
微米银粉 (混合片状棒状银粉，平均粒径5微米) 80重量份；Micron silver powder (mixed sheet-like silver powder, average particle diameter 5 microns) 80 parts by weight;
环氧树脂 (DER354) 9.0重量份；Epoxy resin (DER354) 9.0 parts by weight;
固化剂 (甲基六氢苯酐) 9.0重量份；Curing agent (methyl hexahydrophthalic anhydride) 9.0 parts by weight;
促进剂 (N,N-二甲基苄胺) 0.15重量份；Promoter (N,N-dimethylbenzylamine) 0.15 parts by weight;
偶联剂 (KH-590) 0.15重量份；Coupling agent (KH-590) 0.15 parts by weight;
稀释剂 (2-乙基己基缩水甘油醚) 1重量份；Diluent (2-ethylhexyl glycidyl ether) 1 part by weight;
防沉淀剂 (气相二氧化硅) 0.1重量份；Anti-precipitation agent (fumed silica) 0.1 part by weight;
上述掺杂银盐的导电银胶的制备方法包括以下步骤：The preparation method of the above silver salt-doped conductive silver paste comprises the following steps:
(1)将硝酸银按照所述比例填入环氧树脂中，搅拌研磨，使得银盐充分的分散，制成组分均一的基础树脂A； (1) The silver nitrate is filled into the epoxy resin according to the ratio, stirred and ground, so that the silver salt is sufficiently dispersed to form a base resin A having a uniform composition;
(2)将稀释剂、防沉淀剂、偶联剂、固化剂、促进剂按所述比例添加到基础树脂A中，混合后用三辊研磨机研磨均匀，混合脱泡，制成组分均一的基础树脂B；(2) adding a diluent, an anti-precipitating agent, a coupling agent, a curing agent, and a promoter to the base resin A in the above ratio, mixing and then uniformly grinding with a three-roll mill, mixing and defoaming to prepare a uniform composition. Base resin B;
(3)将银粉按所述比例添加到基础树脂B中，混合均匀后用三辊研磨机研磨，混合脱泡，制成膏状的成品掺杂银盐的导电银胶。(3) The silver powder is added to the base resin B in the above ratio, uniformly mixed, and then ground by a three-roll mill, and mixed and defoamed to form a paste-like conductive silver paste-doped conductive silver paste.
实施例12Example 12
本实施例提供了一种掺杂银盐的导电银胶，是由以下原料制备得到的：This embodiment provides a conductive silver paste doped with a silver salt, which is prepared from the following materials:
银盐 (溴化银) 0.6重量份；Silver salt (silver bromide) 0.6 parts by weight;
微米银粉 (混合片状棒状银粉，平均粒径5微米) 80重量份；Micron silver powder (mixed sheet-like silver powder, average particle diameter 5 microns) 80 parts by weight;
环氧树脂 (DER354) 9.0重量份；Epoxy resin (DER354) 9.0 parts by weight;
固化剂 (甲基六氢苯酐) 9.0重量份；Curing agent (methyl hexahydrophthalic anhydride) 9.0 parts by weight;
促进剂 (N,N-二甲基苄胺) 0.15重量份；Promoter (N,N-dimethylbenzylamine) 0.15 parts by weight;
偶联剂 (KH-590) 0.15重量份；Coupling agent (KH-590) 0.15 parts by weight;
稀释剂 (2-乙基己基缩水甘油醚) 1重量份；Diluent (2-ethylhexyl glycidyl ether) 1 part by weight;
防沉淀剂 (气相二氧化硅) 0.1重量份；Anti-precipitation agent (fumed silica) 0.1 part by weight;
上述掺杂银盐的导电银胶的制备方法包括以下步骤：The preparation method of the above silver salt-doped conductive silver paste comprises the following steps:
(1)将溴化银按照所述比例填入环氧树脂中，搅拌研磨，使得银盐充分的分散，制成组分均一的基础树脂A；(1) The silver bromide is filled into the epoxy resin according to the ratio, stirred and ground, so that the silver salt is sufficiently dispersed to form a base resin A having a uniform composition;
(2)将稀释剂、防沉淀剂、偶联剂、固化剂、促进剂按所述比例添加到基础树脂A中，混合后用三辊研磨机研磨均匀，混合脱泡，制成组分均一的基础树脂B；(2) adding a diluent, an anti-precipitating agent, a coupling agent, a curing agent, and a promoter to the base resin A in the above ratio, mixing and then uniformly grinding with a three-roll mill, mixing and defoaming to prepare a uniform composition. Base resin B;
(3)将银粉按所述比例添加到基础树脂B中，混合均匀后用三辊研磨机研磨，混合脱泡，制成膏状的成品掺杂银盐的导电银胶。(3) The silver powder is added to the base resin B in the above ratio, uniformly mixed, and then ground by a three-roll mill, and mixed and defoamed to form a paste-like conductive silver paste-doped conductive silver paste.
实施例13Example 13
本实施例提供了一种掺杂银盐的导电银胶，是由以下原料制备得到的：This embodiment provides a conductive silver paste doped with a silver salt, which is prepared from the following materials:
银盐 (醋酸银) 0.6重量份；Silver salt (silver acetate) 0.6 parts by weight;
微米银粉 (混合片状棒状银粉，平均粒径5微米) 80重量份；Micron silver powder (mixed sheet-like silver powder, average particle diameter 5 microns) 80 parts by weight;
环氧树脂 (DER354) 9.0重量份；Epoxy resin (DER354) 9.0 parts by weight;
固化剂 (甲基六氢苯酐) 9.0重量份；Curing agent (methyl hexahydrophthalic anhydride) 9.0 parts by weight;
促进剂 (N,N-二甲基苄胺) 0.15重量份；Promoter (N,N-dimethylbenzylamine) 0.15 parts by weight;
偶联剂 (KH-590) 0.15重量份； Coupling agent (KH-590) 0.15 parts by weight;
稀释剂 (2-乙基己基缩水甘油醚) 1重量份；Diluent (2-ethylhexyl glycidyl ether) 1 part by weight;
防沉淀剂 (气相二氧化硅) 0.1重量份；Anti-precipitation agent (fumed silica) 0.1 part by weight;
上述掺杂银盐的导电银胶的制备方法包括以下步骤：The preparation method of the above silver salt-doped conductive silver paste comprises the following steps:
(1)将醋酸银按照所述比例填入环氧树脂中，搅拌研磨，使得银盐充分的分散，制成组分均一的基础树脂A；(1) the silver acetate is filled into the epoxy resin according to the ratio, stirred and ground, so that the silver salt is sufficiently dispersed to form a base resin A having a uniform composition;
(2)将稀释剂、防沉淀剂、偶联剂、固化剂、促进剂按所述比例添加到基础树脂A中，混合后用三辊研磨机研磨均匀，混合脱泡，制成组分均一的基础树脂B；(2) adding a diluent, an anti-precipitating agent, a coupling agent, a curing agent, and a promoter to the base resin A in the above ratio, mixing and then uniformly grinding with a three-roll mill, mixing and defoaming to prepare a uniform composition. Base resin B;
(3)将银粉按所述比例添加到基础树脂B中，混合均匀后用三辊研磨机研磨，混合脱泡，制成膏状的成品掺杂银盐的导电银胶。(3) The silver powder is added to the base resin B in the above ratio, uniformly mixed, and then ground by a three-roll mill, and mixed and defoamed to form a paste-like conductive silver paste-doped conductive silver paste.
实施例14(对比例3)Example 14 (Comparative Example 3)
本实施例提供了一种导电银胶，是由以下原料制备得到的：This embodiment provides a conductive silver paste which is prepared from the following materials:
微米银粉 (混合片状棒状银粉，平均粒径5微米) 80重量份；Micron silver powder (mixed sheet-like silver powder, average particle diameter 5 microns) 80 parts by weight;
环氧树脂 (DER354) 9.3重量份；Epoxy resin (DER354) 9.3 parts by weight;
固化剂 (甲基六氢苯酐) 9.3重量份；Curing agent (methyl hexahydrophthalic anhydride) 9.3 parts by weight;
促进剂 (N,N-二甲基苄胺) 0.15重量份；Promoter (N,N-dimethylbenzylamine) 0.15 parts by weight;
偶联剂 (KH-590) 0.15重量份；Coupling agent (KH-590) 0.15 parts by weight;
稀释剂 (2-乙基己基缩水甘油醚) 1重量份；Diluent (2-ethylhexyl glycidyl ether) 1 part by weight;
防沉淀剂 (气相二氧化硅) 0.1重量份；Anti-precipitation agent (fumed silica) 0.1 part by weight;
上述掺杂银盐的导电银胶的制备方法包括以下步骤：The preparation method of the above silver salt-doped conductive silver paste comprises the following steps:
(1)将稀释剂、防沉淀剂、偶联剂、固化剂、促进剂按所述比例添加到环氧树脂中，混合后用三辊研磨机研磨均匀，混合脱泡，制成组分均一的基础树脂1；(1) adding diluent, anti-precipitating agent, coupling agent, curing agent and accelerator to the epoxy resin in the above ratio, mixing and grinding uniformly with a three-roll mill, mixing and defoaming to prepare a uniform composition Base resin 1;
(2)将微米银粉按所述比例添加到基础树脂1中，混合均匀后用三辊研磨机研磨，混合脱泡，制成膏状的成品导电银胶。(2) The micron silver powder is added to the base resin 1 in the above ratio, mixed uniformly, and then ground by a three-roll mill, and mixed and defoamed to obtain a paste-like finished conductive silver paste.
实施例15Example 15
本实施例提供了一种掺杂银盐的导电银胶，是由以下原料制备得到的：This embodiment provides a conductive silver paste doped with a silver salt, which is prepared from the following materials:
银盐 (醋酸银) 0.2重量份；Silver salt (silver acetate) 0.2 parts by weight;
微米银粉 (混合片状棒状银粉，平均粒径5微米) 80重量份；Micron silver powder (mixed sheet-like silver powder, average particle diameter 5 microns) 80 parts by weight;
环氧树脂 (DER354) 9.2重量份；Epoxy resin (DER354) 9.2 parts by weight;
固化剂 (甲基六氢苯酐) 9.2重量份； Curing agent (methyl hexahydrophthalic anhydride) 9.2 parts by weight;
促进剂 (N,N-二甲基苄胺) 0.15重量份；Promoter (N,N-dimethylbenzylamine) 0.15 parts by weight;
偶联剂 (KH-590) 0.15重量份；Coupling agent (KH-590) 0.15 parts by weight;
稀释剂 (2-乙基己基缩水甘油醚) 1重量份；Diluent (2-ethylhexyl glycidyl ether) 1 part by weight;
防沉淀剂 (气相二氧化硅) 0.1重量份；Anti-precipitation agent (fumed silica) 0.1 part by weight;
上述掺杂银盐的导电银胶的制备方法包括以下步骤：The preparation method of the above silver salt-doped conductive silver paste comprises the following steps:
(1)将醋酸银按照所述比例填入环氧树脂中，搅拌研磨，使得银盐充分的分散，制成组分均一的基础树脂A；(1) the silver acetate is filled into the epoxy resin according to the ratio, stirred and ground, so that the silver salt is sufficiently dispersed to form a base resin A having a uniform composition;
(2)将稀释剂、防沉淀剂、偶联剂、固化剂、促进剂按所述比例添加到基础树脂A中，混合后用三辊研磨机研磨均匀，混合脱泡，制成组分均一的基础树脂B；(2) adding a diluent, an anti-precipitating agent, a coupling agent, a curing agent, and a promoter to the base resin A in the above ratio, mixing and then uniformly grinding with a three-roll mill, mixing and defoaming to prepare a uniform composition. Base resin B;
(3)将银粉按所述比例添加到基础树脂B中，混合均匀后用三辊研磨机研磨，混合脱泡，制成膏状的成品掺杂银盐的导电银胶。(3) The silver powder is added to the base resin B in the above ratio, uniformly mixed, and then ground by a three-roll mill, and mixed and defoamed to form a paste-like conductive silver paste-doped conductive silver paste.
实施例16Example 16
本实施例提供了一种掺杂银盐的导电银胶，是由以下原料制备得到的：This embodiment provides a conductive silver paste doped with a silver salt, which is prepared from the following materials:
银盐 (醋酸银) 0.4重量份；Silver salt (silver acetate) 0.4 parts by weight;
微米银粉 (混合片状棒状银粉，平均粒径5微米) 80重量份；Micron silver powder (mixed sheet-like silver powder, average particle diameter 5 microns) 80 parts by weight;
环氧树脂 (DER354) 9.1重量份；Epoxy resin (DER354) 9.1 parts by weight;
固化剂 (甲基六氢苯酐) 9.1重量份；Curing agent (methyl hexahydrophthalic anhydride) 9.1 parts by weight;
促进剂 (N,N-二甲基苄胺) 0.15重量份；Promoter (N,N-dimethylbenzylamine) 0.15 parts by weight;
偶联剂 (KH-590) 0.15重量份；Coupling agent (KH-590) 0.15 parts by weight;
稀释剂 (2-乙基己基缩水甘油醚) 1重量份；Diluent (2-ethylhexyl glycidyl ether) 1 part by weight;
防沉淀剂 (气相二氧化硅) 0.1重量份；Anti-precipitation agent (fumed silica) 0.1 part by weight;
上述掺杂银盐的导电银胶的制备方法包括以下步骤：The preparation method of the above silver salt-doped conductive silver paste comprises the following steps:
(1)将醋酸银按照所述比例填入环氧树脂中，搅拌研磨，使得银盐充分的分散，制成组分均一的基础树脂A；(1) the silver acetate is filled into the epoxy resin according to the ratio, stirred and ground, so that the silver salt is sufficiently dispersed to form a base resin A having a uniform composition;
(2)将所述稀释剂、防沉淀剂、偶联剂、固化剂、促进剂按所述比例添加到基础树脂A中，混合后使用三辊研磨机研磨均匀，混合脱泡，制成组分均一的基础树脂B；(2) adding the diluent, anti-precipitation agent, coupling agent, curing agent, and accelerator to the base resin A in the above ratio, mixing and grinding uniformly using a three-roll mill, mixing and defoaming, and forming a group a uniform base resin B;
(3)将银粉按所述比例添加到基础树脂B中，混合均匀后用三辊研磨机研磨，混合脱泡，制成膏状的成品掺杂银盐的导电银胶。 (3) The silver powder is added to the base resin B in the above ratio, uniformly mixed, and then ground by a three-roll mill, and mixed and defoamed to form a paste-like conductive silver paste-doped conductive silver paste.
实施例17Example 17
本实施例提供了一种掺杂银盐的导电银胶，是由以下原料制备得到的：This embodiment provides a conductive silver paste doped with a silver salt, which is prepared from the following materials:
银盐 (溴化银：硝酸银＝1:1) 0.6重量份；Silver salt (silver bromide: silver nitrate = 1:1) 0.6 parts by weight;
微米银粉 (混合片状棒状银粉，平均粒径5微米) 80重量份；Micron silver powder (mixed sheet-like silver powder, average particle diameter 5 microns) 80 parts by weight;
环氧树脂 (壳牌双酚A型环氧树脂828E) 17重量份；Epoxy resin (Shell bisphenol A type epoxy resin 828E) 17 parts by weight;
固化剂 (双氰胺) 1重量份；Curing agent (dicyandiamide) 1 part by weight;
促进剂 (1-氰乙基-2-乙基-4-甲基咪唑) 0.1重量份；Promoter (1-cyanoethyl-2-ethyl-4-methylimidazole) 0.1 part by weight;
偶联剂 (KH-560) 0.1重量份；Coupling agent (KH-560) 0.1 parts by weight;
稀释剂 (1,4-丁二醇二缩水甘油醚) 1.15重量份；Diluent (1,4-butanediol diglycidyl ether) 1.15 parts by weight;
防沉淀剂 (气相二氧化硅) 0.05重量份；Anti-precipitation agent (fumed silica) 0.05 parts by weight;
上述掺杂银盐的导电银胶的制备方法包括以下步骤：The preparation method of the above silver salt-doped conductive silver paste comprises the following steps:
(1)将溴化银与硝酸银组成的混合银盐按照所述比例填入环氧树脂中，搅拌研磨，使得银盐充分的分散，制成组分均一的基础树脂A；(1) a mixed silver salt composed of silver bromide and silver nitrate is filled into the epoxy resin according to the ratio, stirred and ground, so that the silver salt is sufficiently dispersed to form a base resin A having a uniform composition;
(2)将稀释剂、防沉淀剂、偶联剂、固化剂、促进剂按所述比例添加到基础树脂A中，混合后用三辊研磨机研磨均匀，混合脱泡，制成组分均一的基础树脂B；(2) adding a diluent, an anti-precipitating agent, a coupling agent, a curing agent, and a promoter to the base resin A in the above ratio, mixing and then uniformly grinding with a three-roll mill, mixing and defoaming to prepare a uniform composition. Base resin B;
(3)将微米银粉按所述比例添加到基础树脂B中，混合均匀后用三辊研磨机研磨，混合脱泡，制成膏状的成品掺杂银盐的导电银胶。(3) The micron silver powder is added to the base resin B in the above ratio, mixed uniformly, and then ground by a three-roll mill, and mixed and defoamed to prepare a paste-like conductive silver paste-doped conductive silver paste.
将银盐以掺杂的方式引入导电银胶配方后，通过银盐与银粉之间的特殊作用，弥补了银粉表面的缺陷，同时形成了银盐纳米团簇，增加了导电填料之间的通路，而且有效地阻止了氧气对银粉表面的氧化，大大提高了可靠性；为了确定本发明制备得到的导电银胶的工作性能，申请人还对实施例1-17制备得到的导电银胶分别进行了测试分析，其测试结果见下表1所示。After the silver salt is doped into the conductive silver paste formulation, the special effect between the silver salt and the silver powder compensates for the defects on the surface of the silver powder, and at the same time, the silver salt nanoclusters are formed, and the path between the conductive fillers is increased. Moreover, the oxidation of the surface of the silver powder by oxygen is effectively prevented, and the reliability is greatly improved; in order to determine the working performance of the conductive silver paste prepared by the present invention, the applicant also separately performs the conductive silver paste prepared in the examples 1-17. Test analysis, the test results are shown in Table 1.
表1Table 1
Figure PCTCN2016101131-appb-000001
Figure PCTCN2016101131-appb-000001
Figure PCTCN2016101131-appb-000002
Figure PCTCN2016101131-appb-000002
从表1中可以看出，相对于没有掺杂银盐的产品(如将实施例3、6进行对比)，达到相同导电性能，所需要的微米银粉大大的降低(降低约20wt％)；掺杂适量的银盐后，在银粉填充量70％、80％时，导电银胶的体积电阻率可以达到10-5数量级，已经达到目前市售导电银胶的较高水平(目前市售导电银胶，如WTS-5101/5102/5106及DK901的体积电阻率一般为10-4数量级；并且在降低导电填料用量的同时，产品的剪切强度有一定程度的提升，如在实施例1-3中，当微米银粉的含量由80％降到60％时，所制备得到的产品的剪切强度从23.10MPa上升到25.21Mpa；此外，银盐的掺杂还可降低导电银胶的渗流阈值，如在双氰胺固化剂体系中添加0.6重量份的硝酸银后，可以使得所制备得到的导电银胶的渗流阈值从15％降到6％。As can be seen from Table 1, the micron silver powder required is greatly reduced (reduced by about 20% by weight) compared to the product not doped with the silver salt (as compared with Examples 3 and 6), achieving the same conductivity. After the appropriate amount of silver salt, the volume resistivity of the conductive silver paste can reach 10 -5 orders of magnitude when the silver powder is filled at 70% and 80%, which has reached the higher level of the currently available conductive silver paste (currently available in the market for conductive silver) The volume resistivity of glues such as WTS-5101/5102/5106 and DK901 is generally on the order of 10 -4 ; and the shear strength of the product is improved to some extent while reducing the amount of conductive filler, as in Examples 1-3. In the case where the content of the micron silver powder is reduced from 80% to 60%, the shear strength of the prepared product is increased from 23.10 MPa to 25.21 MPa; in addition, the doping of the silver salt can also lower the percolation threshold of the conductive silver paste. After adding 0.6 parts by weight of silver nitrate to the dicyandiamide curing agent system, the percolation threshold of the prepared conductive silver paste can be reduced from 15% to 6%.
因此，使用银盐掺杂的这种简单易行的方式，可以使得制备得到的银盐掺杂的导电银胶具有高的导电性能和粘结强度，并且该方法还可以大大节约生产成本，提高产品的市场竞争力，所制备得到的掺杂银盐的导电银胶可广泛应用于太阳能电池、IC和LED封装等领域。 Therefore, the silver salt doped conductive silver paste can have high conductivity and bond strength by using the simple and easy way of doping with silver salt, and the method can also greatly save production cost and improve. The market competitiveness of the products, the prepared silver salt-doped conductive silver paste can be widely used in the fields of solar cells, ICs and LED packages.

Claims (10)

  1. 一种掺杂银盐的导电银胶，其是由以下原料制备得到的：A conductive silver paste doped with a silver salt, which is prepared from the following materials:
    Figure PCTCN2016101131-appb-100001
    Figure PCTCN2016101131-appb-100001
  2. 根据权利要求1所述的掺杂银盐的导电银胶，其特征在于，所述银盐包括硝酸银、醋酸银及卤化银中的一种或几种的组合。The silver salt-doped conductive silver paste according to claim 1, wherein the silver salt comprises one or a combination of silver nitrate, silver acetate, and silver halide.
  3. 根据权利要求1所述的掺杂银盐的导电银胶，其特征在于，所述微米银粉选自片状、球状及棒状银粉中的一种或几种的组合，该微米银粉的尺寸为1～10μm。The silver-doped conductive silver paste according to claim 1, wherein the micron silver powder is selected from one or a combination of a sheet-like, spherical and rod-shaped silver powder having a size of 1 ~10μm.
  4. 根据权利要求1所述的掺杂银盐的导电银胶，其特征在于，所述环氧树脂包括双酚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、耐高温AG-80/90环氧树脂、TDE-85环氧树脂、脂环族环氧树脂及酚醛环氧树脂中的一种或几种的组合。The silver-doped conductive silver paste according to claim 1, wherein the epoxy resin comprises a bisphenol A type epoxy resin, a hydrogenated bisphenol A type epoxy resin, and a bisphenol F type epoxy resin. A combination of one or more of hydantoin epoxy resin, high temperature resistant AG-80/90 epoxy resin, TDE-85 epoxy resin, alicyclic epoxy resin, and novolac epoxy resin.
  5. 根据权利要求1所述的掺杂银盐的导电银胶，其特征在于，所述固化剂包括咪唑类固化剂、咪唑改性物类固化剂、芳香族胺类固化剂、芳香族胺改性物类固化剂、双氰胺类固化剂、双氰胺衍生物类固化剂、酸酐类固化剂、有机酸酰肼固化剂、三氟化硼-胺络合物固化剂、多胺盐固化剂及微胶囊化固化剂中的一种或几种的组合。The silver salt-doped conductive silver paste according to claim 1, wherein the curing agent comprises an imidazole curing agent, an imidazole modified curing agent, an aromatic amine curing agent, and an aromatic amine modification. Material curing agent, dicyandiamide curing agent, dicyandiamide derivative curing agent, acid anhydride curing agent, organic acid hydrazide curing agent, boron trifluoride-amine complex curing agent, polyamine salt curing agent And a combination of one or more of the microencapsulated curing agents.
  6. 根据权利要求1所述的掺杂银盐的导电银胶，其特征在于，所述促进剂包括2,4,6-三(二甲氨基甲基)苯酚、2-乙基-4-甲基咪唑、三苯基膦、1-氰乙基-2-乙基-4-甲基咪唑、N,N-二甲基环己胺、N,N-二甲基苄胺、有机脲、四甲基胍、乙酰丙酮的金属盐、过氧化二苯甲酰及芳基异氰酸酯中的一种或几种的组合。The silver salt-doped conductive silver paste according to claim 1, wherein the accelerator comprises 2,4,6-tris(dimethylaminomethyl)phenol, 2-ethyl-4-methyl Imidazole, triphenylphosphine, 1-cyanoethyl-2-ethyl-4-methylimidazole, N,N-dimethylcyclohexylamine, N,N-dimethylbenzylamine, organic urea, tetramethyl A combination of one or more of a base metal, a metal salt of acetylacetone, dibenzoyl peroxide, and an aryl isocyanate.
  7. 根据权利要求1所述的掺杂银盐的导电银胶，其特征在于，所述偶联剂包括硅烷偶联剂、钛酸酯偶联剂、铝酸酯偶联剂、双金属偶联剂、木质素偶联剂及锡偶联剂中的一种或几种的组合。 The silver salt-doped conductive silver paste according to claim 1, wherein the coupling agent comprises a silane coupling agent, a titanate coupling agent, an aluminate coupling agent, and a bimetallic coupling agent. a combination of one or more of a lignin coupling agent and a tin coupling agent.
  8. 根据权利要求1所述的掺杂银盐的导电银胶，其特征在于，所述稀释剂包括正丁基缩水甘油醚、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、C12/14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及间苯二酚二缩水甘油醚中的一种或几种的组合；The silver salt-doped conductive silver paste according to claim 1, wherein the diluent comprises n-butyl glycidyl ether, 1,4-butanediol diglycidyl ether, trimethylolpropane shrinkage Glycerol ether, glycerol triglycidyl ether, sterol glycidyl ether, ethylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, allyl glycidyl ether, phenyl glycidyl ether, benzyl glycidol Ether, 2-ethylhexyl glycidyl ether, C12/14 alkyl glycidyl ether, diethylene glycol glycidyl ether, p-tert-butyl glycidyl ether, cyclohexanediol diglycidyl ether and resorcinol a combination of one or more of glycidyl ethers;
    优选地，所述防沉淀剂包括气相二氧化硅和/或有机膨润土。Preferably, the anti-precipitation agent comprises fumed silica and/or organic bentonite.
  9. 权利要求1-8任一项所述掺杂银盐的导电银胶的制备方法，其包括以下步骤：The method for preparing a silver salt-doped conductive silver paste according to any one of claims 1-8, comprising the steps of:
    (1)将银盐填入环氧树脂中并使其分散均匀，得到基础树脂A；(1) filling the silver salt into the epoxy resin and dispersing it uniformly to obtain the base resin A;
    (2)将稀释剂、防沉淀剂、偶联剂、固化剂、促进剂添加到所述基础树脂A中，研磨均匀后，混合脱泡，得到基础树脂B；(2) adding a diluent, an anti-precipitating agent, a coupling agent, a curing agent, an accelerator to the base resin A, after grinding uniformly, mixing and defoaming, to obtain a base resin B;
    (3)将微米银粉添加到所述基础树脂B中，研磨均匀后，混合脱泡，得到所述掺杂银盐的导电银胶。(3) Micron silver powder is added to the base resin B, and after grinding uniformly, the mixture is defoamed to obtain the conductive silver paste doped with a silver salt.
  10. 权利要求1-8任一项所述掺杂银盐的导电银胶作为半导体电子封装材料的应用。 The use of the silver salt-doped conductive silver paste of any of claims 1-8 as a semiconductor electronic packaging material.
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CN113817426B (en) * 2021-08-25 2023-06-30 上海锐朗光电材料有限公司 Conductive adhesive applied to large-size chip bonding and preparation method thereof
CN113897152A (en) * 2021-10-11 2022-01-07 刘东海 High-temperature-resistant conductive silver adhesive and preparation method thereof

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