CN110607142B - Conductive silver paste pressure-sensitive adhesive and preparation method thereof - Google Patents

Conductive silver paste pressure-sensitive adhesive and preparation method thereof Download PDF

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CN110607142B
CN110607142B CN201911041485.8A CN201911041485A CN110607142B CN 110607142 B CN110607142 B CN 110607142B CN 201911041485 A CN201911041485 A CN 201911041485A CN 110607142 B CN110607142 B CN 110607142B
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nano
emulsion
stirring
silver paste
sensitive adhesive
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CN110607142A (en
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齐登武
吴卫均
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Enping Yingjiafeng Adhesive Products Co ltd
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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
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives 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
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • 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
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/385—Acrylic polymers
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    • 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
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2227—Oxides; Hydroxides of metals of aluminium
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2265—Oxides; Hydroxides of metals of iron
    • C08K2003/2272—Ferric oxide (Fe2O3)
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    • 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
    • C08K2201/011—Nanostructured additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
    • 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
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/302—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive being pressure-sensitive, i.e. tacky at temperatures inferior to 30°C
    • 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
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/314—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive layer and/or the carrier being conductive

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  • Adhesives Or Adhesive Processes (AREA)

Abstract

The conductive silver paste pressure-sensitive adhesive comprises the following raw materials in parts by weight: 50-80 parts of composite emulsion, 7-10 parts of nano filler, 7-10 parts of fumed silica, 4-7 parts of water-based wetting dispersant, 1-2 parts of curing accelerator, 30-40 parts of conductive silver paste, 0.8-1 part of coupling agent, 0.5-0.7 part of antioxidant and 0.3-0.6 part of sterilization and mildew inhibitor, wherein the composite emulsion comprises styrene-butadiene latex, acrylate emulsion and polyether modified organic silicon defoamer, and the nano filler consists of nano boron oxide, nano aluminum oxide and nano iron oxide. The pressure-sensitive adhesive disclosed by the invention takes the blended emulsion of the water-based styrene-butadiene latex and the acrylate emulsion as a main body of the pressure-sensitive adhesive, is supplemented with the conductive silver paste filler, the nano filler and the gas-phase white carbon black, and the filler is uniformly dispersed, so that the pressure-sensitive adhesive has high bonding performance, electric conductivity and thermal conductivity.

Description

Conductive silver paste pressure-sensitive adhesive and preparation method thereof
Technical Field
The invention relates to the technical field of pressure-sensitive adhesives, in particular to a conductive silver paste pressure-sensitive adhesive and a preparation method thereof.
Background
The conductive adhesive is a special adhesive which can effectively bond various materials after being cured or dried and has conductive performance. Compared with the traditional metal solder Pb/Sn, the conductive adhesive is free of lead and other toxic metals, is environment-friendly, has low curing temperature, is suitable for thermosensitive materials and non-weldable materials, can be used for connecting and fixing tiny components, and is suitable for assembling precise components; the treatment steps are simple, and the processing cost is reduced; the adhesive is suitable for bonding surfaces and reduces stress concentration. The conductive adhesive contains metal fillers with conductive performance, and copper, aluminum, zinc, iron and nickel fillers have low resistivity, but are easy to generate oxidation and chemical corrosion or electrochemical corrosion in the using process, so that the resistance stability is poor; and the filler is easy to settle in a polymer body, so that the distribution of the filler is uneven, and the conductivity of the filler is seriously influenced.
Meanwhile, with the development of microelectronic products towards high density and high speed, for example, the generation of 5G technology, an electronic component must have larger electric power, most functions of an electronic system begin to be integrated into a single chip, the heat generation amount also gradually increases, the circuit temperature of the chip continuously rises, and the chip has the defects of short service life, poor reliability and the like, so that the conductive pressure-sensitive adhesive is urgently needed to have good heat resistance and must have good heat conductivity.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, provides the environment-friendly conductive silver paste pressure-sensitive adhesive with high bonding performance, good operation manufacturability, good electrical conductivity and thermal conductivity and strong environmental adaptability, and also provides a preparation method of the pressure-sensitive adhesive.
The invention is realized by the following technical scheme:
the conductive silver paste pressure-sensitive adhesive comprises the following raw materials in parts by weight: 80-120 parts of composite emulsion, 7-10 parts of nano filler, 7-10 parts of fumed silica, 4-7 parts of water-based wetting dispersant, 1-2 parts of curing accelerator, 30-40 parts of conductive silver paste, 0.8-1 part of coupling agent, 0.5-0.7 part of antioxidant and 0.3-0.6 part of bactericidal mildew preventive.
Further, the water-based wetting dispersant is BYK-152 water-based polyacrylate wetting dispersant. The polyacrylic ammonium salt dispersing agent is a polymer dispersing agent modified by hydrophobic property, can effectively reduce viscosity, improves storage stability and leveling property, and has higher dispersibility than common water-resistant dispersing agents, so that the consumption is low and the dispersing effect is good.
Further, the curing accelerator is one of vanadium acetylacetonate, tetramethylthiourea, triphenylphosphine, acetylacetone, and n-butyl aldehyde-aniline condensate 808. The curing accelerator can promote the crosslinking of active groups in the styrene-butadiene latex and the acrylic emulsion and improve the cohesive force of the pressure-sensitive adhesive.
Furthermore, the antioxidant is one of antioxidant 1010, antioxidant MB and antioxidant 168, and can improve the aging resistance of the pressure-sensitive adhesive; the sterilization mildew preventive is N-octyl isothiazolinone or 2-methyl-4-isothiazolinone-3-ketone. The coupling agent is one of vinyl trimethoxy silane, vinyl triacetoxy silane, vinyl triethoxy silane or vinyl tri-tert-butyl peroxy silane.
Further, the conductive silver paste is prepared by the following method: adding silver powder into the acrylate emulsion, uniformly mixing, standing and eliminating bubbles to obtain the acrylic acid acrylate emulsion; the weight ratio of the acrylate emulsion to the deionized water to the silver powder is 10: 3: (2-3). Silver occupies a major position in conductive fillers because of its good conductive properties, stable properties, and good conductivity even if its product, silver oxide, is oxidized. According to the invention, the conductive silver paste filler is added into the raw materials of the pressure-sensitive adhesive, the conductive silver paste filler has good fluidity and wettability, and can penetrate into cavities and cracks to enable the interior of an adhesive layer to be more compact, so that the volume shrinkage generated by colloid cracking is effectively inhibited.
Further, the composite emulsion comprises styrene-butadiene latex, acrylate emulsion and polyether modified organic silicon defoamer, and the weight ratio of the styrene-butadiene latex to the acrylate emulsion is 2: 3: (0.01-0.02) and can be other types of defoaming agents, and the type and the dosage of the defoaming agents are based on the purpose of defoaming. The conductive pressure-sensitive adhesive disclosed by the invention adopts the composite emulsion as a pressure-sensitive adhesive matrix, the composite emulsion is a mixture of the acrylate emulsion and the aqueous styrene-butadiene latex, the styrene-butadiene latex contains carboxylic acid, and the polarity of a molecular chain is improved, so that the cohesiveness of the styrene-butadiene latex is improved, the styrene-butadiene latex is low in cost, environment-friendly and safe, but the problems of low drying speed, poor initial adhesion performance, poor conductive performance, further improved stability and the like still exist; the acrylate emulsion has the advantages of good film forming property, adhesion, transparency, weather resistance and the like, the acrylate emulsion and the water-based styrene-butadiene latex have good compatibility, and the performance defects of the styrene-butadiene latex, such as poor conductivity, initial adhesion, wet bonding effect and the like, can be improved by mixing and modifying the acrylate emulsion with the water-based styrene-butadiene latex to obtain the blending composite emulsion with excellent performance; meanwhile, the acrylate monomers are various in types and have large performance difference, so that the molecular design of the acrylate polymer product is strong, and the product with ideal performance can be obtained by controlling the types, the content, the auxiliary agents and the like of the monomers.
Further, the composite emulsion is prepared by the following method: taking a certain amount of acrylate emulsion, and adjusting the pH value of the emulsion to 9-10 by using ammonia water; taking a certain amount of styrene-butadiene latex, and adjusting the pH value of the emulsion to 9-10 by using a dilute boric acid solution with the mass fraction of 5%; and slowly adding the styrene-butadiene latex into the acrylate emulsion under the stirring condition of 300-320 r/min, stirring for 100-110 min, adding the polyether modified organic silicon defoamer, continuously stirring for 16-20 min, and filtering with 150-mesh filter cloth to obtain the composite emulsion.
Further, the nano filler comprises a mixture of nano boron oxide, nano aluminum oxide and nano iron oxide in a mass ratio of 10 (6-7) to 0.8-1, and the mesh number of filler particles is larger than 800 meshes. The pressure-sensitive adhesive taking silver as a main conductive filler has high conductivity, but on one hand, the silver is expensive, on the other hand, the silver has high density and is easy to settle in a system, and although the anti-settling property of the pressure-sensitive adhesive can be improved by reducing the size of the nano silver, the aggregation phenomenon of nano particles is more serious along with the reduction of the particle size, and the dispersion and the performance of the pressure-sensitive adhesive are influenced. In addition, the nano-filler is dispersed in the pressure-sensitive adhesive structure, and a network structure is formed in the system due to the large surface area, so that the nano-filler becomes a conductive channel and a heat conduction path, and the nano-filler further improves the electrical conductivity and the heat conductivity while balancing the cost.
Further, the nanofiller is prepared by the steps of:
s1, adding the nano boron oxide, the nano aluminum oxide and the nano iron oxide which are mixed according to the proportion into 50% concentrated sulfuric acid, placing the mixture into a water bath kettle at the temperature of 60 ℃, stirring the mixture for 2 hours at the speed of 300r/min, and quickly placing the reaction liquid into an ice water bath after the stirring is finished to obtain a nano filler suspension;
s2, centrifuging the suspension obtained in the step S1 at 10000rpm for 10min, removing supernatant, performing suction filtration on the rest suspension, washing the precipitate with distilled water for 3-4 times, and then dripping 1-2 mL of NaHCO3Continuously adding distilled water into the solution for centrifugal treatment to enable the pH value of the nanofiller suspension at the lower layer to be 6-7, and collecting the suspension at the lower layer;
s3, carrying out ultrasonic treatment on the suspension obtained in the step S2 for 30min to obtain nano filler, concentrating the volume of the nano filler to 1/3 of the original volume by using a rotary evaporator, freeze-drying the concentrated solution, grinding the dried nano particles, and then sieving the ground nano particles with a 800-mesh sieve to obtain the nano filler.
The nano filler prepared by the method can be firmly combined with the fumed silica, has a firm net structure in the pressure-sensitive adhesive, improves the strength of the pressure-sensitive adhesive, and enhances the bonding performance of the pressure-sensitive adhesive.
The preparation method of the conductive silver paste pressure-sensitive adhesive comprises the following steps:
s1, placing the composite emulsion in a planetary stirrer, starting stirring, adding the nano filler, stirring for 25-30 min, and then vacuumizing and defoaming; continuously adding fumed silica and the water-based wetting dispersant, continuously stirring for 10-15 min, closing a cylinder cover of the planetary stirrer after the edge is shoveled, vacuumizing and defoaming, controlling the vacuum degree to be not higher than-0.1 MPa, stirring for 15-20 min, and discharging to obtain a component A;
s2, adding the curing accelerator and the coupling agent into a planetary stirrer, stirring for 10-12 min, and vacuumizing and defoaming; continuously adding conductive silver paste, an antioxidant and a sterilization mildew inhibitor, continuously stirring for 10-15 min, closing a cylinder cover of the planetary stirrer after edge shoveling, vacuumizing and defoaming, controlling the vacuum degree to be not higher than-0.1 MPa, stirring for 16-18 min, and discharging to obtain a component B;
and S3, mixing the component A and the component B according to the mass ratio, and stirring at 260r/min for 45-50 min to obtain the conductive silver paste pressure-sensitive adhesive.
The preparation method of the conductive silver paste comprises the following steps: adding deionized water as little as possible into the acrylate emulsion to dissolve the acrylate emulsion, adding silver powder, mixing uniformly, standing and eliminating bubbles to obtain the acrylic acid acrylate emulsion.
The composite emulsion is prepared by the following method: taking a certain amount of acrylate emulsion, and adjusting the pH value of the emulsion to 9-10 by using ammonia water; taking a certain amount of styrene-butadiene latex, and adjusting the pH value of the emulsion to 9-10 by using a dilute boric acid solution with the mass fraction of 5%; and slowly adding the styrene-butadiene latex into the acrylate emulsion under the stirring condition of 300-320 r/min, stirring for 100-110 min, adding the polyether modified organic silicon defoamer, continuously stirring for 16-20 min, and filtering with 150-mesh filter cloth to obtain the composite emulsion.
The nano filler is prepared by uniformly mixing 10 (6-7) by mass of nano boron oxide, 0.8-1) by mass of nano aluminum oxide and nano iron oxide, and then grinding and sieving with a 800-mesh sieve.
The nano filler is prepared by the following steps:
s1, adding the nano boron oxide, the nano aluminum oxide and the nano iron oxide which are mixed according to the proportion into 50% concentrated sulfuric acid, heating to 60 ℃, stirring for 2 hours under the condition of 300r/min, and quickly putting the reaction liquid into an ice-water bath after stirring to obtain a nano filler suspension;
s2, centrifuging the suspension obtained in the step S1 at 10000r/min for 10min, removing supernatant, carrying out suction filtration on the rest suspension, washing the precipitate with distilled water for 3-4 times, and then dripping 1-2 mL of NaHCO3Continuously adding distilled water into the solution for centrifugal treatment to enable the pH value of the nanofiller suspension at the lower layer to be 6-7, and collecting the suspension at the lower layer;
s3, carrying out ultrasonic treatment on the suspension obtained in the step S2 for 30min to obtain nano filler, concentrating the volume of the nano filler to 1/3 of the original volume by using a rotary evaporator, freeze-drying the concentrated solution, grinding the dried nano particles, and then sieving the ground nano particles with a 800-mesh sieve to obtain the nano filler.
According to the pressure-sensitive adhesive, the blending modified emulsion of the water-based styrene-butadiene rubber latex and the acrylate emulsion is used as a main body of the pressure-sensitive adhesive, and the conductive silver paste filler, the nano filler and the gas-phase white carbon black are used as auxiliary materials, so that the prepared pressure-sensitive adhesive is conductive and has high bonding performance; meanwhile, the pressure-sensitive adhesive is endowed with good corrosion resistance and aging resistance through the addition of the antioxidant and the sterilization mildewproof agent in a trace amount; the preparation method of the water-based wetting dispersant, the coupling agent and the nano filler can ensure that the conductive filler in the pressure-sensitive adhesive is well and uniformly dispersed without sedimentation, and is beneficial to the exertion of the conductive performance; the nanometer filler with good heat conductivity and the silver particles are filled, so that the heat conductivity of the pressure-sensitive adhesive is improved. The pressure-sensitive adhesive prepared by the invention has the advantages of high adhesive property, good operation manufacturability, good thermal conductivity and strong environmental adaptability.
Detailed Description
The conductive silver paste pressure-sensitive adhesive comprises the following raw materials in parts by weight: 80-120 parts of composite emulsion, 7-10 parts of nano filler, 7-10 parts of fumed silica, 4-7 parts of water-based wetting dispersant, 1-2 parts of curing accelerator, 30-40 parts of conductive silver paste, 0.8-1 part of coupling agent, 0.5-0.7 part of antioxidant and 0.3-0.6 part of bactericidal mildew preventive.
The water-based wetting dispersant is BYK-152 water-based polyacrylate wetting dispersant. The curing accelerator is one of vanadium acetylacetonate, tetramethyl thiourea, triphenylphosphine, acetylacetone and n-butyl aldehyde-aniline condensate 808. The antioxidant is one of antioxidant 1010, antioxidant MB and antioxidant 168, and can improve the aging resistance of the pressure-sensitive adhesive; the sterilization mildew preventive is N-octyl isothiazolinone or 2-methyl-4-isothiazolinone-3-ketone. The coupling agent is one of vinyl trimethoxy silane, vinyl triacetoxy silane, vinyl triethoxy silane or vinyl tri-tert-butyl peroxy silane
The conductive silver paste is prepared by the following method: adding silver powder into the acrylate emulsion, uniformly mixing, standing and eliminating bubbles to obtain the acrylic acid acrylate emulsion; the weight ratio of the acrylate emulsion to the deionized water to the silver powder is 10: 3: (2-3).
The composite emulsion comprises styrene-butadiene latex, acrylate emulsion and polyether modified organic silicon defoamer, and the weight ratio of the styrene-butadiene latex to the acrylate emulsion is 2: 3: (0.01-0.02).
The composite emulsion is prepared by the following method: taking a certain amount of acrylate emulsion, and adjusting the pH value of the emulsion to 9-10 by using ammonia water; taking a certain amount of styrene-butadiene latex, and adjusting the pH value of the emulsion to 9-10 by using a dilute boric acid solution with the mass fraction of 5%; and slowly adding the styrene-butadiene latex into the acrylate emulsion under the stirring condition of 300-320 r/min, stirring for 100-110 min, adding the polyether modified organic silicon defoamer, continuously stirring for 16-20 min, and filtering with 150-mesh filter cloth to obtain the composite emulsion.
The nano filler comprises a mixture of nano boron oxide, nano aluminum oxide and nano iron oxide in a mass ratio of 10 (6-7) to 0.8-1, and the mesh number of filler particles is larger than 800 meshes.
The nano filler is prepared by the following steps:
s1, adding the nano boron oxide, the nano aluminum oxide and the nano iron oxide which are mixed according to the proportion into 50% concentrated sulfuric acid, placing the mixture into a water bath kettle at the temperature of 60 ℃, stirring the mixture for 2 hours at the speed of 300r/min, and quickly placing the reaction liquid into an ice water bath after the stirring is finished to obtain a nano filler suspension;
s2, centrifuging the suspension obtained in the step S1 at 10000r/min for 10min, removing supernatant, carrying out suction filtration on the rest suspension, washing the precipitate with distilled water for 3-4 times, and then dripping 1-2 mL of NaHCO3Continuously adding distilled water into the solution for centrifugal treatment to enable the pH value of the nanofiller suspension at the lower layer to be 6-7, and collecting the suspension at the lower layer;
s3, carrying out ultrasonic treatment on the suspension obtained in the step S2 for 30min to obtain nano filler, concentrating the volume of the nano filler to 1/3 of the original volume by using a rotary evaporator, freeze-drying the concentrated solution, grinding the dried nano particles, and then sieving the ground nano particles with a 800-mesh sieve to obtain the nano filler.
The preparation method of the conductive silver paste pressure-sensitive adhesive comprises the following steps:
s1, placing the composite emulsion in a planetary stirrer, starting stirring, adding the nano filler, stirring for 25-30 min, and then vacuumizing and defoaming; continuously adding fumed silica and the water-based wetting dispersant, continuously stirring for 10-15 min, closing a cylinder cover of the planetary stirrer after the edge is shoveled, vacuumizing and defoaming, controlling the vacuum degree to be not higher than-0.1 MPa, stirring for 15-20 min, and discharging to obtain a component A;
s2, adding the curing accelerator and the coupling agent into a planetary stirrer, stirring for 10-12 min, and vacuumizing and defoaming; continuously adding conductive silver paste, an antioxidant and a sterilization mildew inhibitor, continuously stirring for 10-15 min, closing a cylinder cover of the planetary stirrer after edge shoveling, vacuumizing and defoaming, controlling the vacuum degree to be not higher than-0.1 MPa, stirring for 16-18 min, and discharging to obtain a component B;
and S3, mixing the component A and the component B according to the mass ratio, and stirring at 260r/min for 45-50 min to obtain the conductive silver paste pressure-sensitive adhesive.
The preparation method of the conductive silver paste comprises the following steps: adding silver powder into the acrylate emulsion, uniformly mixing, standing and eliminating bubbles to obtain the acrylic acid acrylate emulsion.
The composite emulsion is prepared by the following method: taking a certain amount of acrylate emulsion, and adjusting the pH value of the emulsion to 9-10 by using ammonia water; taking a certain amount of styrene-butadiene latex, and adjusting the pH value of the emulsion to 9-10 by using a dilute boric acid solution with the mass fraction of 5%; and slowly adding the styrene-butadiene latex into the acrylate emulsion under the stirring condition of 300-320 r/min, stirring for 100-110 min, adding the polyether modified organic silicon defoamer, continuously stirring for 16-20 min, and filtering with 150-mesh filter cloth to obtain the composite emulsion.
The nano filler is prepared by uniformly mixing 10 (6-7) by mass of nano boron oxide, 0.8-1) by mass of nano aluminum oxide and nano iron oxide, and then grinding and sieving with a 800-mesh sieve.
The nano filler is prepared by the following steps:
s1, adding the nano boron oxide, the nano aluminum oxide and the nano iron oxide which are mixed according to the proportion into 50% concentrated sulfuric acid, heating to 60 ℃, stirring for 2 hours under the condition of 300r/min, and quickly putting the reaction liquid into an ice-water bath after stirring to obtain a nano filler suspension;
s2, centrifuging the suspension obtained in the step S1 at 10000r/min for 10min, removing supernatant, carrying out suction filtration on the rest suspension, washing the precipitate with distilled water for 3-4 times, and then dripping 1-2 mL of NaHCO3Continuously adding distilled water into the solution for centrifugal treatment to enable the pH value of the nanofiller suspension at the lower layer to be 6-7, and collecting the suspension at the lower layer;
s3, carrying out ultrasonic treatment on the suspension obtained in the step S2 for 30min to obtain nano filler, concentrating the volume of the nano filler to 1/3 of the original volume by using a rotary evaporator, freeze-drying the concentrated solution, grinding the dried nano particles, and then sieving the ground nano particles with a 800-mesh sieve to obtain the nano filler.
The contents of the components of examples 1 to 3 are shown in Table 1.
Table 1 component formulations of examples 1-3
Figure BDA0002252280530000101
Figure BDA0002252280530000111
Example 1
The styrene-butadiene latex in the composite emulsion is BASF styrene-butadiene emulsion SD-417, and the acrylate emulsion is BASF acrylate emulsion V215; the weight ratio of the acrylate emulsion to the deionized water to the silver powder in the conductive silver paste is 10: 3: 3; the mass ratio of the nanometer boron oxide, the nanometer aluminum oxide and the nanometer ferric oxide in the nanometer filler is 10: 6: 1; the curing accelerator is vanadium acetylacetonate; the antioxidant is an antioxidant 1010; the sterilization mildew preventive is N-octyl isothiazolinone; the coupling agent is vinyl trimethoxy silane.
Example 2
The styrene-butadiene latex in the composite emulsion is BASF styrene-butadiene latex SD332, and the emulsion is Rohm and Hass acrylic ester emulsion 2468; the weight ratio of the acrylate emulsion, the deionized water and the silver powder in the conductive silver paste is 10: 3: 2.8 of; the mass ratio of the nanometer boron oxide, the nanometer aluminum oxide and the nanometer ferric oxide in the nanometer filler is 10: 6.5: 0.9; the curing accelerator is tetramethyl thiourea; the antioxidant is antioxidant 168; the bactericidal mildew preventive is 2-methyl-4-isothiazoline-3-ketone; the coupling agent is vinyl triacetoxysilane.
Example 3
The styrene-butadiene latex in the composite emulsion is Dow styrene-butadiene latex DL313, and the acrylate emulsion is BASF acrylate emulsion S537; the weight ratio of the acrylate emulsion, the deionized water and the silver powder in the conductive silver paste is 10: 3: 2.5; the mass ratio of the nanometer boron oxide, the nanometer aluminum oxide and the nanometer ferric oxide in the nanometer filler is 10: 7: 0.8; the curing accelerator is triphenylphosphine; the antioxidant is antioxidant MB; the bactericidal mildew preventive is 2-methyl-4-isothiazoline-3-ketone; the coupling agent is vinyl triethoxysilane.
Effect evaluation and Performance detection
According to the following preparation steps, the conductive silver paste adhesive tape is prepared from the conductive silver paste pressure-sensitive adhesive and is subjected to the following performance tests:
and (1) paving a substrate film on a flat and smooth glass plate, fixing two ends of the substrate film by using adhesive tapes, pouring the obtained conductive silver paste pressure-sensitive adhesive on one end of the film, slowly and uniformly pushing the conductive silver paste pressure-sensitive adhesive to the other end of the film from the end by using a scraper, uniformly paving the adhesive on the film, and controlling the adhesive.
And (2) standing at room temperature for 30min, then drying in a 110 ℃ air-blast constant-temperature drying oven for 10min, cooling, and then pasting the release paper on the adhesive surface for later use to be tested.
Pressure sensitive adhesive initial adhesion, permanent adhesion and 180-degree peel strength performance test
The conductive silver paste tapes of examples 1 to 3 were subjected to performance tests, respectively, and the test items included: initial tack (GB/T4852-2002), tack strength (GB/T4851-1998) and 180 ℃ peel strength (GB/T2792-1998). Accordingly, the results of the tests on the tack strength and 180 ° peel strength properties under the same conditions using a commercially available ordinary adhesive tape as a comparative example are shown in table 1.
TABLE 1 test results for examples 1-3
Performance index Example 1 Example 2 Example 3 Comparative example
180 degree peel strength (N/25mm) 25.02 25.53 25.32 15.56
Initial viscosity (ball number #) 8 9 8 5
Viscosity (Hr) ≥24 ≥24 ≥24 ≥12
As shown in Table 1, the initial adhesion, the permanent adhesion and the 180-degree peel strength of the flame-retardant conductive acrylate pressure-sensitive adhesive tape are superior to those of the common adhesive tape.
The above detailed description is specific to possible embodiments of the present invention, and the embodiments are not intended to limit the scope of the present invention, and all equivalent implementations or modifications that do not depart from the scope of the present invention are intended to be included within the scope of the present invention.

Claims (6)

1. The conductive silver paste pressure-sensitive adhesive is characterized by comprising the following raw materials in parts by weight: 80-120 parts of composite emulsion, 7-10 parts of nano filler, 7-10 parts of fumed silica, 4-7 parts of water-based wetting dispersant, 1-2 parts of curing accelerator, 30-40 parts of conductive silver paste, 0.8-1 part of coupling agent, 0.5-0.7 part of antioxidant and 0.3-0.6 part of sterilizing and mildew-proofing agent;
the conductive silver paste is prepared by the following method: adding silver powder into the acrylate emulsion, uniformly mixing, standing and eliminating bubbles to obtain the acrylic acid acrylate emulsion; the weight ratio of the acrylate emulsion to the deionized water to the silver powder is 10: 3: (2-3);
the composite emulsion comprises styrene-butadiene latex, acrylate emulsion and polyether modified organic silicon defoamer, and the weight ratio of the styrene-butadiene latex to the acrylate emulsion is 2: 3: (0.01-0.02);
the nano filler comprises a mixture of nano boron oxide, nano aluminum oxide and nano iron oxide in a mass ratio of 10 (6-7) (0.8-1), and the mesh number of filler particles is more than 800 meshes;
the nano filler is prepared by the following steps:
s1, adding the nano boron oxide, the nano aluminum oxide and the nano iron oxide which are mixed according to the proportion into 50% concentrated sulfuric acid, heating to 60 ℃, stirring for 2 hours under the condition of 300r/min, and quickly putting the reaction liquid into an ice-water bath after stirring to obtain a nano filler suspension;
s2, centrifuging the suspension obtained in the step S1 at 10000r/min for 10min, removing supernatant, carrying out suction filtration on the rest suspension, washing the precipitate with distilled water for 3-4 times, and then dripping 1-2 mL of NaHCO3Continuously adding distilled water into the solution for centrifugal treatment to enable the pH value of the nanofiller suspension at the lower layer to be 6-7, and collecting the suspension at the lower layer;
s3, carrying out ultrasonic treatment on the suspension obtained in the step S2 for 30min, then concentrating the volume to 1/3 of the original volume by using a rotary evaporator, carrying out freeze drying on the concentrated solution, grinding the dried nanoparticles, and then sieving with a 800-mesh sieve to obtain the nano filler.
2. The conductive silver paste pressure-sensitive adhesive as claimed in claim 1, wherein the aqueous wetting dispersant is a BYK-152 aqueous polyacrylate wetting dispersant.
3. The conductive silver paste pressure-sensitive adhesive as claimed in claim 1, wherein the curing accelerator is one of vanadium acetylacetonate, tetramethylthiourea, triphenylphosphine, acetylacetone, and n-butylaldehyde-aniline condensate 808.
4. The conductive silver paste pressure-sensitive adhesive as claimed in claim 1, wherein the antioxidant is one of antioxidant 1010, antioxidant MB and antioxidant 168; the sterilization mildew preventive is N-octyl isothiazolinone or 2-methyl-4-isothiazolinone-3-ketone; the coupling agent is one of vinyl trimethoxy silane, vinyl triacetoxy silane, vinyl triethoxy silane or vinyl tri-tert-butyl peroxy silane.
5. The conductive silver paste pressure-sensitive adhesive as claimed in claim 1, wherein the composite emulsion is prepared by the following method: taking a certain amount of acrylate emulsion, and adjusting the pH value of the emulsion to 9-10 by using ammonia water; taking a certain amount of styrene-butadiene latex, and adjusting the pH value of the emulsion to 9-10 by using a dilute boric acid solution with the mass fraction of 5%; and slowly adding the styrene-butadiene latex into the acrylate emulsion under the stirring condition of 300-320 r/min, stirring for 100-110 min, adding the polyether modified organic silicon defoamer, continuously stirring for 16-20 min, and filtering with 150-mesh filter cloth to obtain the composite emulsion.
6. The preparation method of the conductive silver paste pressure-sensitive adhesive according to claim 1, comprising the following steps:
s1, placing the composite emulsion in a planetary stirrer, starting stirring, adding the nano filler, stirring for 25-30 min, and then vacuumizing and defoaming; continuously adding fumed silica and the water-based wetting dispersant, continuously stirring for 10-15 min, closing a cylinder cover of the planetary stirrer after the edge is shoveled, vacuumizing and defoaming, controlling the vacuum degree to be not higher than-0.1 MPa, stirring for 15-20 min, and discharging to obtain a component A;
s2, adding the curing accelerator and the coupling agent into a planetary stirrer, stirring for 10-12 min, and vacuumizing and defoaming; continuously adding conductive silver paste, an antioxidant and a sterilization mildew inhibitor, continuously stirring for 10-15 min, closing a cylinder cover of the planetary stirrer after edge shoveling, vacuumizing and defoaming, controlling the vacuum degree to be not higher than-0.1 MPa, stirring for 16-18 min, and discharging to obtain a component B;
s3, mixing the component A and the component B according to the mass ratio, and stirring at 260r/min for 45-50 min to obtain the conductive silver paste pressure-sensitive adhesive;
the preparation method of the conductive silver paste comprises the following steps: adding silver powder into the acrylate emulsion, uniformly mixing, standing and eliminating bubbles to obtain the acrylic acid acrylate emulsion;
the composite emulsion is prepared by the following method: taking a certain amount of acrylate emulsion, and adjusting the pH value of the emulsion to 9-10 by using ammonia water; taking a certain amount of styrene-butadiene latex, and adjusting the pH value of the emulsion to 9-10 by using a dilute boric acid solution with the mass fraction of 5%; then slowly adding the styrene-butadiene latex into the acrylate emulsion under the stirring condition of 300-320 r/min, stirring for 100-110 min, adding the polyether modified organic silicon defoamer, continuously stirring for 16-20 min, and filtering with 150-mesh filter cloth to obtain a composite emulsion;
the nano filler is prepared by the following steps:
s1, adding the nano boron oxide, the nano aluminum oxide and the nano iron oxide which are mixed according to the proportion into 50% concentrated sulfuric acid, heating to 60 ℃, stirring for 2 hours under the condition of 300r/min, and quickly putting the reaction liquid into an ice-water bath after stirring to obtain a nano filler suspension;
s2, centrifuging the suspension obtained in the step S1 at 10000r/min for 10min, removing supernatant, carrying out suction filtration on the rest suspension, washing the precipitate with distilled water for 3-4 times, and then dripping 1-2 mL of NaHCO3Continuously adding distilled water into the solution for centrifugal treatment to enable the pH value of the nanofiller suspension at the lower layer to be 6-7, and collecting the suspension at the lower layer;
s3, carrying out ultrasonic treatment on the suspension obtained in the step S2 for 30min to obtain nano filler, concentrating the volume of the nano filler to 1/3 of the original volume by using a rotary evaporator, freeze-drying the concentrated solution, grinding the dried nano particles, and then sieving the ground nano particles with a 800-mesh sieve to obtain the nano filler.
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