CN111440562A - Modified conductive filler, preparation method thereof and conductive adhesive - Google Patents
Modified conductive filler, preparation method thereof and conductive adhesive Download PDFInfo
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- CN111440562A CN111440562A CN202010311019.3A CN202010311019A CN111440562A CN 111440562 A CN111440562 A CN 111440562A CN 202010311019 A CN202010311019 A CN 202010311019A CN 111440562 A CN111440562 A CN 111440562A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 23
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- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 2
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Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
- C09J9/02—Electrically-conducting adhesives
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J179/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09J161/00 - C09J177/00
- C09J179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- C08K2201/001—Conductive additives
-
- 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
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
-
- 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
- C08K2201/002—Physical properties
- C08K2201/004—Additives being defined by their length
-
- 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
- C08K2201/011—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
- C08L2205/03—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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Conductive Materials (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention provides a modified conductive filler, a preparation method thereof and a conductive adhesive, and belongs to the technical field of conductive fillers. The invention utilizes-OH groups generated by the hydrolysis of a silane coupling agent to form surface chemical bonding with the nano silver wire particle interface; activity of the other end of the coupling agent-NH2Reacts with-OCN group in cyanate monomer to form modified conductive filler with terminal-OCN reaction activity anchored chain structure. The result shows that after the conductive filler is prepared into the conductive adhesive, the curing temperature is 170 +/-20 ℃, the curing time is 60 +/-20 min, and the conductive filler has excellent temperature resistance (Tg is more than 210 ℃) and conductivity (the volume resistivity is less than 10)‑4Omega cm), heat conduction (more than 8W/m.K) and mechanical properties (the shear strength is more than or equal to 13.76MPa, and the bending strength is more than or equal to 58.43 MPa).
Description
Technical Field
The invention relates to the technical field of conductive fillers, in particular to a modified conductive filler, a preparation method thereof and a conductive adhesive.
Background
The conductive adhesive used as a bonding functional component generally consists of polymer resin, filler and functional auxiliary agent. Among them, the polymer resin mainly plays roles in adhesion, molding of integrated circuit devices and components, and stabilizing of assembly structures, and the like, and the polymer resin is required to have excellent properties such as adhesion, mechanics, heat resistance, processing technology and the like. The filler plays a role in constructing an electric conduction channel and a heat conduction channel, ensures effective passing of electrons and phonons, and has the characteristics of low resistivity, high heat conductivity coefficient, difficult oxidation and the like, thereby ensuring the realization of electric conduction and heat dissipation functions.
The conductive filler widely used in the current market is silver powder. The characteristics of low resistivity, high thermal conductivity, difficult oxidation and the like of silver make the silver an ideal conductive material adopted by the current conductive adhesive, but in order to obtain better conductivity, the addition of the silver usually needs to exceed 75 wt%, even 90 wt%, and the cost of the conductive adhesive material is high. And excessive addition leads the silver powder formed in the conductive adhesive to settle and be unevenly distributed in the long-term storage process, thus leading the electric conduction and the heat dissipation performance to be poor and even leading the mechanical properties of the solidified product, such as the impact strength, and the like to be influenced.
Based on the current situation, the patent CN109929490A adopts thermoplastic alcohol-soluble acrylic resin as matrix resin to prepare the silver-based conductive adhesive for the L CD screen, the adhesive force of the silver-based conductive adhesive and a glass substrate is good, a curing agent is not required to be added for curing reaction, and the silver-based conductive adhesive has the advantages of long service life, small volume resistivity, strong adhesive force and the like.
Although the method improves the conductive filler in different ways, improves the storage performance and the dispersion performance of the conductive adhesive, and reduces the production cost of the conductive adhesive, the conductive adhesive has poor temperature resistance, and cannot meet the use requirements in the field of high-temperature (not less than 200 ℃) electronic components. With the application and development of the 5G communication technology, electronic components running at high speed and high frequency bear larger impact load and emit more heat, and the conductive adhesive is required to have more excellent temperature resistance, high-temperature mechanical dynamic performance and bonding stability, and the conductive adhesive prepared by the conventional method cannot meet the requirements on temperature resistance. The development and application of new conductive filler to prepare the conductive adhesive for high-speed and high-frequency components is the key to promote the application of the conductive adhesive for the miniature electronic components in the 5G field.
Disclosure of Invention
The invention aims to provide a modified conductive filler, a preparation method thereof and a conductive adhesive.
In order to achieve the above object, the present invention provides the following technical solutions:
a preparation method of a modified conductive filler comprises the following steps:
1) mixing the nano silver wire, a silane coupling agent and a mixed solvent, and carrying out hydrolysis reaction to obtain a hydrolysis valence bond adsorption modified nano silver wire;
2) mixing the hydrolysis valence bond adsorption modified nano silver wire obtained in the step 1) with a cyanate monomer and an organic solvent, and carrying out in-situ grafting reaction to obtain the modified conductive filler.
Preferably, the mixed solvent in the step 1) comprises ethanol and water, and the mass ratio of the ethanol to the water is 2-5: 1.
preferably, the hydrolysis reaction in step 1) is performed under ultrasonic conditions.
Preferably, the length of the silver nanowire in the step 1) is 40-80 μm, and the diameter of the silver nanowire is 150-250 nm.
Preferably, the silane coupling agent in step 1) is an aminosilane coupling agent.
Preferably, the cyanate ester monomer in step 2) is a bisphenol pentaerythritol cinnamaldehyde type cyanate ester monomer.
Preferably, the temperature of the in-situ grafting reaction in the step 2) is 90-120 ℃, and the time of the in-situ grafting reaction is 2-5 hours.
The invention also provides the modified conductive filler prepared by the preparation method, which comprises a nano silver wire, an-OH group grafted on the surface of the nano silver wire and a terminal-OCN (optically active carbon) reactive anchoring chain structure.
The invention also provides a conductive adhesive prepared by using the modified conductive filler.
Preferably, the conductive adhesive comprises the following components in parts by mass: 100 parts of cyanate ester monomer, 5-15 parts of toughening modifier, 18-50 parts of modified conductive filler, 0.01-0.05 part of functional assistant, 0.5-2 parts of thickener, 0.1-0.5 part of defoamer and 30-110 parts of solvent.
The invention provides a modified conductive fillerThe preparation method of the material comprises the following steps: mixing the nano silver wire, a silane coupling agent and a mixed solvent, and carrying out hydrolysis reaction to obtain a hydrolysis valence bond adsorption modified nano silver wire; and mixing the obtained hydrolysis valence bond adsorption modified nano silver wire with a cyanate monomer and an organic solvent, and carrying out in-situ grafting reaction to obtain the modified conductive filler. The method utilizes-OH groups generated by hydrolysis of a silane coupling agent to form surface chemical bonding with the nano silver wire particle interface; activity of the other end of the coupling agent-NH2Reacts with one-OCN group in cyanate monomer to form modified conductive filler with terminal-OCN reactive 'anchor' chain structure. When the modified conductive filler prepared by the preparation method provided by the invention is used, in-situ grafting reaction between-OCN groups in a matrix resin monomer is carried out to form a grafting chain segment between a nano silver wire and glue solution main body resin, and the chemical bonding binding effect of the grafting chain segment can effectively realize in-situ uniform dispersion of the conductive filler in a resin matrix frame, prevent the conductive filler in a glue solution system from settling, and construct a high-efficiency conductive and heat dissipation channel. Experimental results show that after the conductive filler prepared by the method is used for preparing the conductive adhesive, the curing temperature is 170 +/-20 ℃, the curing time is 60 +/-20 min, and the conductive adhesive has excellent temperature resistance (Tg is more than 210 ℃) and conductivity (the volume resistivity is less than 10)-4Omega cm), heat conduction (more than 8W/m.K) and mechanical properties (the shear strength is more than or equal to 13.76MPa, and the bending strength is more than or equal to 58.43 MPa).
Drawings
FIG. 1 is a FT-IR spectrum of a bisphenol pentaerythritol cinnamyl aldehyde type cyanate monomer in application example 8 of the present invention;
FIG. 2 is an SEM image of a cured product of the conductive adhesive of application example 8 of the present invention;
FIG. 3 shows the DMA test results of the cured conductive adhesive of application example 8 of the present invention.
Detailed Description
The invention provides a preparation method of a modified conductive filler, which comprises the following steps:
1) mixing the nano silver wire, a silane coupling agent and a mixed solvent, and carrying out hydrolysis reaction to obtain a hydrolysis valence bond adsorption modified nano silver wire;
2) mixing the hydrolysis valence bond adsorption modified nano silver wire obtained in the step 1) with a cyanate monomer and an organic solvent, and carrying out in-situ grafting reaction to obtain the modified conductive filler.
According to the invention, the nano silver wire, the silane coupling agent and the mixed solvent are mixed, and hydrolysis reaction is carried out to obtain the hydrolysis valence bond adsorption modified nano silver wire. In the invention, the silane coupling agent undergoes hydrolysis reaction, and the generated-OH group and the nano silver wire particle interface form surface chemical bonding.
In the invention, the length of the nano silver wire is preferably 20-100 μm, more preferably 40-80 μm, and most preferably 50-60 μm; the diameter of the nano silver wire is preferably 100-350 nm, more preferably 120-300 nm, and most preferably 150-250 nm. In the invention, the nano silver wire can generate hydrolysis reaction with the silane coupling agent, and the generated-OH group and the nano silver wire particle interface form surface chemical bonding. The invention limits the size of the nano silver wire in the range, and can further improve the filling effect of the conductive filler. The source of the silver nanowires in the present invention is not particularly limited, and commercially available products known to those skilled in the art may be used.
In the present invention, the silane coupling agent is preferably an aminosilane coupling agent, and more preferably γ -aminopropyltriethoxysilane. In the invention, the silane coupling agent can perform hydrolysis reaction to provide-OH groups, so that surface chemical bonding is formed with the nano silver wire particle interface. The source of the silane coupling agent in the present invention is not particularly limited, and commercially available products known to those skilled in the art may be used.
In the present invention, the mixed solvent is preferably ethanol and water; the mass ratio of the ethanol to the water is preferably 2-5: 1, more preferably 3: 1. in the invention, the mixed solvent is used as a solvent, and can provide a reaction environment for the hydrolysis reaction of the nano silver wire and the silane coupling agent.
In the invention, the mass ratio of the nano silver wire, the silane coupling agent and the mixed solvent is preferably (1-2): (1-2): (40-60), more preferably 1: 1: 50. the invention limits the dosage of each component in the range, can ensure the full contact of the nano silver wire and the silane coupling agent in the modification process, simultaneously can not cause the waste of raw materials, and saves the production cost.
In the present invention, the hydrolysis reaction is preferably performed under ultrasonic conditions. The invention has no limitation on the instruments used in the ultrasonic process, and only needs to use a common ultrasonic disperser.
The mixing mode of the nano silver wire, the silane coupling agent and the mixed solvent is not particularly limited, and the method for mixing materials, which is well known to those skilled in the art, can be adopted. In the invention, the mixing of the nano silver wire, the silane coupling agent and the mixed solvent is preferably to add the nano silver wire into the mixed solvent, then continue the ultrasonic oscillation in an ultrasonic container, finally drop the silane coupling agent into the mixed system in the oscillation state, and carry out the ultrasonic oscillation hydrolysis. By adopting the mode, the nano silver wires and the silane coupling agent can be subjected to hydrolysis reaction fully, and the modification efficiency is further improved.
In the present invention, the time of the hydrolysis reaction is preferably 6 to 10 hours, and more preferably 8 hours.
After the hydrolysis reaction is finished, the invention preferably carries out solid-liquid separation, washing and drying on the products of the hydrolysis reaction in sequence to obtain the hydrolysis valence bond adsorption modified nano silver wire. In the invention, the washing is preferably carried out by firstly carrying out centrifugal washing on the mixture for 3-6 times, more preferably 5 times, by using deionized water, and then carrying out centrifugal washing on the mixture for 2-4 times, more preferably 3 times, by using absolute ethyl alcohol. In the present invention, the drying is preferably vacuum drying; the drying temperature is preferably 100-150 ℃; the drying time is preferably 2-5 hours.
After the hydrolysis valence bond adsorption modified nano silver wire is obtained, the hydrolysis valence bond adsorption modified nano silver wire is mixed with a cyanate ester monomer and an organic solvent, and the modified conductive filler is obtained through in-situ grafting reaction.
In the present invention, the cyanate ester monomer is preferably a bisphenol pentaerythritol cinnamyl aldehyde type cyanate ester monomer; the structural formula of the bisphenol pentaerythritol cinnamyl aldehyde type cyanate monomer is shown as a formula I:
the source of the cyanate ester monomer is not particularly limited in the present invention, and commercially available products known to those skilled in the art may be used. In the present invention, the cyanate ester monomer is preferably bisphenol pentaerythritol cinnamaldehyde type cyanate ester monomer prepared in example 6 of patent CN 109096300A.
In the invention, the modified nano silver wire and the cyanate ester monomer are subjected to in-situ grafting reaction, and the activity-NH at the other end of the aminosilane coupling agent2The ethylene-vinyl acetate copolymer and one-OCN group in a cyanate monomer form an anchored chain structure with end-OCN reactivity, and the chemical bonding and binding effect of a grafting chain segment can effectively realize the in-situ uniform dispersion of the conductive filler in a resin matrix frame, prevent the conductive filler in a glue solution system from settling, construct an efficient conductive and heat dissipation channel, and effectively avoid the influence of the filler settling and dispersion on the conductive and heat dissipation performance.
In the present invention, the type of the organic solvent is not particularly limited, and the cyanate ester monomer may be dissolved therein. In the present invention, the organic solvent is preferably N, N-dimethylformamide.
In the invention, the mass ratio of the hydrolyzed valence bond adsorption modified nano silver wire, the cyanate ester monomer and the organic solvent is preferably 2: (1-3): (15-30), more preferably 1: 1: 20. the invention limits the dosage of each component in the range, can ensure the full contact of the raw materials in the in-situ grafting reaction process, simultaneously can not cause the waste of the raw materials, and saves the production cost.
The mixing mode of the hydrolyzed valence bond adsorption modified nano silver wire, the cyanate ester monomer and the organic solvent is not particularly limited, and the technical scheme of material mixing, which is well known to those skilled in the art, is adopted. In the invention, the mixture of the hydrolyzed valence bond adsorption modified nano silver wire, the cyanate ester monomer and the organic solvent is preferably: dissolving and dispersing cyanate ester monomers by using an organic solvent, stirring in a heated high-speed emulsification and shearing reaction kettle, and then adding hydrolysis valence bond adsorption modified nano silver wires. By adopting the mixing mode, the hydrolysis valence bond adsorption modified nano silver wire, the cyanate ester monomer and the organic solvent can be fully mixed, the in-situ grafting reaction is accelerated, and the reaction efficiency is further improved.
In the invention, the temperature of the in-situ grafting reaction is preferably 90-120 ℃, and more preferably 110 ℃; the time of the in-situ grafting reaction is preferably 2-5 hours, and more preferably 3 hours. The method controls the temperature of the in-situ grafting reaction within the range, can ensure the normal operation of the in-situ grafting reaction, controls the reaction time within the range, can ensure the full operation of the in-situ grafting reaction, can avoid overlong time and wasting time, and reduces the production cost.
After the in-situ grafting reaction is finished, the product of the in-situ grafting reaction is preferably subjected to solid-liquid separation, washing and drying in sequence to obtain the modified conductive filler. In the invention, the washing is preferably performed by using acetone for centrifugal washing for 3-5 times, and more preferably 4 times. In the present invention, the washing can remove the cyanate ester monomer and part of the N, N-dimethylformamide which do not participate in the reaction. In the present invention, the drying is preferably vacuum drying; the drying temperature is preferably 30-70 ℃, more preferably 50 ℃, and the drying time is preferably 3-5 hours, more preferably 4 hours.
The invention also provides the modified conductive filler prepared by the technical scheme, which comprises a nano silver wire, an-OH group grafted on the surface of the nano silver wire and a terminal-OCN (optically active carbon) reactive anchoring chain structure.
In the invention, the length of the modified conductive filler is preferably 20-100 μm, more preferably 40-80 μm, and most preferably 50-60 μm; the diameter of the modified conductive filler is preferably 100-350 nm, more preferably 120-300 nm, and most preferably 150-250 nm.
In the present invention, the modified conductive filler is preferably hermetically preserved.
The invention also provides a conductive adhesive, and the modified conductive filler is used as a conductive filler.
In the present invention, the conductive adhesive preferably includes, by mass: 100 parts of cyanate ester monomer, 5-15 parts of toughening modifier, 18-50 parts of modified conductive filler, 0.01-0.05 part of functional assistant, 0.5-2 parts of thickener, 0.1-0.5 part of defoamer and 30-110 parts of solvent.
In the present invention, the conductive adhesive preferably includes 100 parts by mass of a cyanate ester monomer. In the present invention, the cyanate ester monomer preferably includes bisphenol pentaerythritol cinnamaldehyde type cyanate ester monomer. The cyanate monomer is used as a matrix resin monomer, a resin network structure of the conductive adhesive is formed after self-crosslinking curing, and the resin has excellent temperature resistance, bonding performance, dimensional stability and humidity resistance, and can be used for a long time in a high-temperature environment of more than 200 ℃.
In the invention, the conductive adhesive preferably comprises 5-15 parts of toughening modifier, more preferably 7-12 parts, and most preferably 10 parts by mass of cyanate ester monomer as 100 parts. In the invention, the toughening modifier is preferably amino-terminated polyether; the amino-terminated polyether is preferably a light yellow viscous liquid; the relative molecular mass of the toughening modifier is preferably 2000-8000, and more preferably 5000. The invention uses the toughening modifier, can further improve the toughness of the resin, so as to meet the impact action of high-speed and high-frequency load, effectively prevent the debonding of the bonding layer caused by the impact action, and improve the bonding performance of the conductive adhesive.
In the invention, the conductive adhesive preferably comprises 18-50 parts of modified conductive filler, more preferably 20-48 parts, and most preferably 40 parts by mass of cyanate ester monomer as 100 parts by mass. In the invention, in-situ grafting reaction between-OCN groups occurs in the modified conductive filler and the matrix resin monomer to form a graft chain segment between the nano silver wire and the glue solution main body resin, and the chemical bonding constraint effect of the graft chain segment can effectively realize in-situ uniform dispersion of the conductive filler in a resin matrix frame, prevent the conductive filler in a glue solution system from settling, and construct a high-efficiency conductive and heat dissipation channel.
In the invention, the conductive adhesive preferably comprises 0.01-0.05 part of functional auxiliary agent, more preferably 0.02 part, by mass of cyanate ester monomer as 100 parts. In the present invention, the functional aid is preferably an organotin additive, more preferably a dibutyltin dilaurate catalyst. The addition of the functional assistant can improve the curing reaction rate of the resin monomer at the curing temperature and shorten the curing time.
In the invention, the conductive adhesive preferably comprises 0.5-2 parts of thickening agent by mass, and more preferably 1.5 parts. In the present invention, the thickener is preferably a compound of hydroxymethylcellulose and polyamide wax; the mass ratio of the hydroxymethylcellulose to the polyamide wax is preferably 1: (1-3), more preferably 1: 2. the thixotropic property of the conductive adhesive can be improved by adding the thickening agent, the construction process is improved, and the solvent used by the adhesive is N, N-dimethylformamide and acetone, so that the thickening effect and the thixotropy of a single component in the solvent are poor, and the thickening and the thixotropy effects can be good after compounding.
In the invention, the conductive adhesive preferably comprises 0.1-0.5 part of defoaming agent, more preferably 0.3 part, based on 100 parts of cyanate ester monomer. In the present invention, the defoaming agent is preferably a BYK-141 silicone defoaming agent. The invention uses the defoaming agent, and can eliminate the phenomena of air bubbles, shrinkage cavities and the like generated in the processes of sizing, solvent volatilization and curing reaction.
In the invention, the conductive adhesive preferably comprises 30-110 parts of solvent, and more preferably 55 parts, by mass of the cyanate ester monomer as 100 parts. In the present invention, the solvent is preferably a complex of N, N-dimethylformamide and acetone; the mass ratio of the N, N-dimethylformamide to the acetone is preferably (1-3): 1, more preferably 2: 1. in the invention, the mixed solvent can provide a solution type reaction medium environment, dilute and reduce viscosity, improve the fluidity of the glue solution and the dispersibility of the solid filler. The co-solubility of the matrix resin and related components can be improved by compounding the high-boiling-point N, N-dimethylformamide and the low-boiling-point acetone; the volatilization rate at low temperature is increased, the solvent residue at the curing temperature is avoided, the curing performance of the adhesive is improved, and the foaming and pinhole phenomena are reduced.
In the present invention, the method for preparing the conductive adhesive preferably comprises the steps of:
(1) mixing a cyanate ester monomer, a toughening modifier and N, N-dimethylformamide to obtain a mixture I;
(2) mixing the mixture I obtained in the step (1) with a modified conductive filler to obtain a mixture II;
(3) mixing the mixture II obtained in the step (2) with a functional additive to perform an in-situ prepolymerization reaction to obtain a mixture III;
(4) and (4) mixing the mixture III obtained in the step (3) with acetone, a thickening agent and a defoaming agent to obtain a conductive adhesive product.
In the invention, preferably, a cyanate ester monomer, a toughening modifier and N, N-dimethylformamide are mixed to obtain a mixture I. In the invention, the cyanate ester monomer, the toughening modifier and the N, N-dimethylformamide are preferably mixed in a manner that the cyanate ester monomer is dissolved and dispersed in the N, N-dimethylformamide to form a transparent solution, then the transparent solution is stirred, and then the toughening modifier is added. By adopting the mode, the cyanate ester monomer and the toughening modifier can be uniformly dispersed, and the modification efficiency is improved.
In the invention, the mixing temperature of the cyanate ester monomer, the toughening modifier and the N, N-dimethylformamide is preferably 50-100 ℃, and more preferably 65-80 ℃; the mixing condition is preferably stirring, and the stirring speed is preferably 50-200 rpm, more preferably 100 rpm. According to the invention, the stirring temperature and the stirring speed of the mixing are controlled within the above ranges, so that the components can be uniformly mixed, and the reaction among the components of the system can be prevented.
After obtaining the mixture i, the present invention preferably mixes the mixture i with the modified conductive filler to obtain the mixture ii. In the present invention, the mixing condition of the mixture I and the modified conductive filler is preferably stirring, and the stirring speed is preferably 1200 +/-50 rpm; the stirring time is preferably 0.2 to 1 hour, and more preferably 0.5 hour. The present invention can further promote the uniform dispersion of the filler in the system and prevent the sedimentation by controlling the stirring rate and the stirring time within the above ranges.
After the mixture II is obtained, the mixture II is preferably mixed with a functional auxiliary agent to carry out in-situ prepolymerization reaction to obtain a mixture III. In the invention, the temperature of the in-situ prepolymerization reaction is preferably 100-150 ℃, and more preferably 110-120 ℃; the time of the in-situ prepolymerization reaction is preferably 1-4 hours, and more preferably 1.5-2.5 hours. The invention can lead-OCN group and-NH to be generated among the toughening modifier, the cyanate monomer and the modified nano silver wire in the system by controlling the reaction temperature and the reaction time in the range2The pre-polymerization and grafting chemical reaction is generated between the-OCN groups, the reaction is completely carried out, and the self-crosslinking curing reaction between the-OCN groups is prevented.
After the in-situ prepolymerization reaction is finished, the temperature of the product of the in-situ prepolymerization reaction is preferably reduced to obtain a mixture III. In the invention, the final temperature of the temperature reduction is preferably 30-70 ℃, and more preferably 45-60 ℃.
After the mixture III is obtained, the mixture III is preferably mixed with acetone, a thickening agent and a defoaming agent to obtain a conductive adhesive product. In the invention, the mixture III is preferably mixed with acetone, a thickening agent and a defoaming agent and refluxed at constant temperature at the acetone reflux temperature; the refluxing time is preferably 0.2 to 1 hour, and more preferably 0.5 hour. According to the invention, through mixing under the conditions, the phenomena of bumping and kettle spraying caused by adding the solvent at a high temperature can be avoided, and the components are mixed more fully and uniformly by reflux stirring at the acetone reflux temperature.
In the conductive adhesive provided by the invention, the curing process of the cyanate monomer belongs to a self-crosslinking type, and the conductive adhesive prepared by taking the cyanate monomer as matrix resin can be cured and crosslinked at a certain temperature without adding a curing agent component, so that the problems of gelation and pot life existing in the process of normal-temperature storage and use of the adhesive are avoided; the cured resin has a triazine ring unit network structure, and triazine ring units are orderly arranged through the linkage of ether bond blocks, so that the conductive adhesive has high temperature resistance (Tg is more than or equal to 210 ℃) and sufficient toughness and bonding performance, and the adhesive is ensured to be in high-temperature and high-speed conditionsThe product can be used for a long time in a high-frequency load environment; the method adopts the silver nanowires with high length-diameter ratio as conductive fillers, realizes the anchoring between the silver nanowires and a cured resin network through in-situ grafting-prepolymerization reaction, and enables the conductive and heat-conducting paths between the fillers in the resin to be changed from point contact (spherical) and discontinuous line contact (flaky or dendritic) into continuous lapping point contact between lines, thereby forming continuous linear conductive and heat-conducting channels, effectively preventing the conductive fillers in a glue solution system from settling, avoiding the influence of the settling and dispersion of the fillers on the conductive and heat dissipation performance, improving the conductive and heat dissipation efficiency of the adhesive, reducing the addition of the conductive fillers and reducing the production cost of the conductive adhesive; the curing temperature of the conductive adhesive provided by the invention is 170 +/-20 ℃, the curing time is 60 +/-20 min, and the conductive adhesive has excellent temperature resistance (Tg is more than 210 ℃) and conductivity (the volume resistivity is less than 10)-4Omega cm), heat conduction (more than 8W/m.K) and mechanical properties (the shear strength is more than or equal to 13.76MPa, the bending strength is more than or equal to 58.43MPa), and the material can be used for a long time in a high-temperature, high-speed and high-frequency load environment.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
1) Adding 1 part by mass of a nano silver wire with the length of 50-60 mu m and the diameter of 150-250 nm into 50 parts of a mixed solvent consisting of ethanol and water (mass ratio 3: 1) performing the following steps;
2) putting the solution into an ultrasonic container for continuous ultrasonic oscillation;
3) dropwise adding 1 part by mass of gamma-aminopropyltriethoxysilane to a solution system in an oscillation state by using a dropper, and carrying out ultrasonic oscillation hydrolysis for 8 hours;
4) centrifugally separating the solution to obtain a crude nano silver wire product subjected to hydrolysis valence bond adsorption modification treatment;
5) centrifugally washing the product with deionized water for 5 times, and centrifugally washing with absolute ethyl alcohol for 3 times;
6) putting the washed product into a vacuum oven at 120 ℃, and drying for 3 hours to obtain a modified nano silver wire;
7) dissolving and dispersing 1 part by mass of bisphenol pentaerythritol cinnamyl aldehyde type cyanate ester monomer by using 20 parts by mass of N, N-dimethylformamide, adding the obtained solution into a high-speed emulsification and shearing reaction kettle capable of being heated, and stirring the obtained product at the rotating speed of 100 rpm;
8) adding 1 part by mass of modified nano silver wire into a solution system, adjusting the shearing speed to 1500rpm, gradually heating to 110 ℃, and reacting at constant temperature for 3 hours;
9) cooling to room temperature, and carrying out centrifugal separation on the reaction liquid to obtain bisphenol pentaerythritol cinnamyl aldehyde type cyanate monomer grafted modified conductive filler;
10) centrifugally washing the modified conductive filler for 5 times by using acetone, and removing unreacted cyanate ester monomers and part of N, N-dimethylformamide;
11) and (3) putting the washed sample into a vacuum oven at 50 ℃, drying for 4 hours to obtain the modified conductive filler with the length of 50-60 mu m and the diameter of 150-250 nm, and sealing and storing.
Application example 1
The conductive adhesive comprises the following components in parts by mass: 100 parts of cyanate ester monomer, 5 parts of toughening modifier, 18 parts of modified conductive filler, 0.01 part of functional additive, 0.5 part of thickener, 0.1 part of defoamer and 55 parts of solvent.
The cyanate monomer is bisphenol pentaerythritol cinnamaldehyde type cyanate monomer, the appearance of the cyanate monomer is faint yellow viscous liquid, and the structural formula of the bisphenol pentaerythritol cinnamaldehyde type cyanate monomer is shown as a formula I:
the toughening modification is amino-terminated polyether, yellowish viscous liquid, and Mn is 5000;
the modified conductive filler is prepared in the embodiment 1, the diameter is 150-250 nm, and the length is 40-80 μm;
the functional additive is a dibutyltin dilaurate catalyst, and the appearance of the functional additive is a light yellow transparent solution;
the thickening agent is prepared from hydroxymethyl cellulose and polyamide wax according to a mass ratio of 1: 2;
the defoaming agent is a BYK-141 organic silicon defoaming agent;
the solvent is N, N-dimethylformamide and acetone according to a mass ratio of 2: 1;
1) dissolving and dispersing 100 parts of bisphenol pentaerythritol cinnamyl aldehyde type cyanate ester monomer by 36.7 parts of N, N-dimethyl amide to obtain a transparent solution;
2) transferring the solution into a high-speed shearing emulsification reaction kettle capable of heating, starting a stirring device, stirring at a low speed (100rpm) at a certain rotating speed, and heating to 82 ℃;
3) weighing 5 parts of amine-terminated polyether, adding the amine-terminated polyether into a reaction kettle in a dropwise manner, and stirring at constant temperature for 0.5h at the current temperature;
4) weighing 18 parts of modified nano silver wires, adding the modified nano silver wires into a reaction kettle, adjusting the stirring speed to 1200rpm, and dispersing for 0.5h at constant temperature;
5) gradually heating the reaction kettle to 110 ℃, adding 0.01 part of dibutyltin dilaurate, carrying out in-situ prepolymerization reaction for 2.5h under the conditions of constant temperature and constant speed, and stopping the reaction;
6) slowly cooling to 50 ℃, adding 0.5 part of thickening agent, 0.1g of defoaming agent and 18.3 parts of acetone, and refluxing for 0.5h at the constant temperature of acetone reflux;
7) cooling to room temperature, and discharging to obtain the conductive adhesive product.
Application example 2
The conductive adhesive comprises the following components in parts by mass: 100 parts of cyanate ester monomer, 15 parts of toughening modifier, 50 parts of silver nanowire, 0.05 part of functional additive, 2 parts of thickener, 0.5 part of defoamer and 55 parts of solvent.
The types and preparation methods of the components in the application examples are the same as those in application example 1.
Application example 3
The conductive adhesive comprises the following components in parts by mass: 100 parts of cyanate ester monomer, 10 parts of toughening modifier, 40 parts of silver nanowire, 0.02 part of functional additive, 1.5 parts of thickener, 0.3 part of defoamer and 55 parts of solvent.
The types and preparation methods of the components in the application examples are the same as those in application example 1.
Application example 4
The conductive adhesive comprises the following components in parts by mass: 100 parts of cyanate ester monomer, 5 parts of toughening modifier, 40 parts of silver nanowire, 0.02 part of functional additive, 1.5 parts of thickener, 0.3 part of defoamer and 55 parts of solvent.
The types and preparation methods of the components in the application examples are the same as those in application example 1.
Application example 5
The conductive adhesive comprises the following components in parts by mass: 100 parts of cyanate ester monomer, 15 parts of toughening modifier, 40 parts of silver nanowire, 0.02 part of functional additive, 1.5 parts of thickener, 0.3 part of defoamer and 55 parts of solvent.
The types and preparation methods of the components in the application examples are the same as those in application example 1.
Application example 6
The conductive adhesive comprises the following components in parts by mass: 100 parts of cyanate ester monomer, 10 parts of toughening modifier, 20 parts of silver nanowire, 0.02 part of functional additive, 1.5 parts of thickener, 0.3 part of defoamer and 55 parts of solvent.
The types and preparation methods of the components in the application examples are the same as those in application example 1.
Application example 7
The conductive adhesive comprises the following components in parts by mass: 100 parts of cyanate ester monomer, 10 parts of toughening modifier, 28 parts of silver nanowire, 0.02 part of functional additive, 1.5 parts of thickener, 0.3 part of defoamer and 55 parts of solvent.
The types and preparation methods of the components in the application examples are the same as those in application example 1.
Application example 8
The conductive adhesive comprises the following components in parts by mass: 100 parts of cyanate ester monomer, 10 parts of toughening modifier, 37 parts of silver nanowire, 0.02 part of functional additive, 1.5 parts of thickener, 0.3 part of defoamer and 55 parts of solvent.
The types and preparation methods of the components in the application examples are the same as those in application example 1.
Application example 9
The conductive adhesive comprises the following components in parts by mass: 100 parts of cyanate ester monomer, 10 parts of toughening modifier, 48 parts of silver nanowire, 0.02 part of functional additive, 1.5 parts of thickener, 0.3 part of defoamer and 55 parts of solvent.
The types and preparation methods of the components in the application examples are the same as those in application example 1.
Characterization and Performance testing
First, infrared spectrum characterization analysis
The infrared spectrum of the bisphenol pentaerythritol cinnamyl aldehyde type cyanate ester monomer is shown in the attached figure 1. Located at 3057.01cm-1、3025.73cm-1The absorption peak is the stretching vibration peak of-CH-group in the benzene ring structure; located at 2955.46cm-1、2886.06cm-1The absorption peak at (A) is assigned to-CH2-stretching vibration absorption peak of-CH-group; a stretching vibration absorption peak of-C.ident.N group in-OCN at 2267.65 cm-1; located at 1597.23cm-1、1492.56cm-1、1452.09cm-1The absorption peak is attributed to the stretching vibration peak of the benzene ring framework; located at 1157.27cm-1The absorption peak belongs to a-C-O-C stretching vibration absorption peak; located at 1243.65cm-1、1060.96cm-1The absorption peak is attributed to the-C-O-group stretching vibration absorption peak in-OCN of cinnamaldehyde type cyanate; the results indicate that the product is a bisphenol pentaerythritol cinnamaldehyde type cyanate ester monomer. Located at 1714.06cm-1、1574.57cm-1、1367.58cm-1The absorption peak is the absorption peak of-C-O (rearrangement), -N-C-O-, -O-groups in a trimer (triazine ring) structure formed by the self-polymerization reaction of the bisphenol cinnamaldehyde cyanate monomer. At the same time at 3427.92cm-1A weak and wide-OH group stretching vibration absorption peak still appears, which indicates that the product contains a small amount of phenol impurities and self-product polymeric impurities.
Second, performance of conductive adhesive
1) The viscosity test is carried out on an NDJ-7 type rotational viscometer of Shanghai Yulong instrument Limited by adopting a rotational viscosity method according to the national standard GB/T22235-;
2) the mechanical property test is carried out according to GB/T2567-2008: the bending strength and the shearing strength are carried out on a Shenzhen New Miss CMT-6503 type microcomputer control electronic universal tensile testing machine, and the loading speed is 2 mm/min;
3) the volume resistivity is measured on a GEST-123 volume resistivity tester of Beijing crown electrical instrument for measuring precision, instruments and equipment Limited, according to QJ1523-1988, and the test requires that the sample size is 50mm × 5mm × 0.5.5 mm, the substrate base material is glass, and the terminal electrode is copper foil.
4) The heat conductivity coefficient is measured on a TC-3000 general type heat conductivity coefficient tester of Xian Xianhui electronic technology Limited according to GB/T10297-2015, and the sample size is phi 25mm × 3 mm.
Table 1 results of performance test of conductive adhesive of application examples 1 to 9
As can be seen from Table 1, the curing temperature of the conductive adhesive prepared by using the modified conductive filler provided by the invention in application examples 1-9 is 170 +/-20 ℃, the curing time is 60 +/-20 min, and the conductive adhesive has excellent temperature resistance (Tg is more than 210 ℃) and conductivity (volume resistivity is less than 10)-4Omega cm), heat conduction (more than 8W/m.K) and mechanical properties (the shear strength is more than or equal to 13.76MPa, and the bending strength is more than or equal to 58.43 MPa).
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A preparation method of a modified conductive filler comprises the following steps:
1) mixing the nano silver wire, a silane coupling agent and a mixed solvent, and carrying out hydrolysis reaction to obtain a hydrolysis valence bond adsorption modified nano silver wire;
2) mixing the hydrolysis valence bond adsorption modified nano silver wire obtained in the step 1) with a cyanate monomer and an organic solvent, and carrying out in-situ grafting reaction to obtain the modified conductive filler.
2. The preparation method according to claim 1, wherein the mixed solvent in the step 1) comprises ethanol and water, and the mass ratio of the ethanol to the water is 2-5: 1.
3. the method according to claim 1, wherein the hydrolysis reaction in step 1) is performed under ultrasonic conditions.
4. The preparation method according to claim 1, wherein the length of the silver nanowires in step 1) is 40 to 80 μm, and the diameter of the silver nanowires is 150 to 250 nm.
5. The production method according to claim 1, wherein the silane coupling agent in step 1) is an aminosilane coupling agent.
6. The method according to claim 1, wherein the cyanate ester monomer in step 2) is a bisphenol pentaerythritol cinnamaldehyde type cyanate ester monomer.
7. The preparation method according to claim 1, wherein the temperature of the in-situ grafting reaction in the step 2) is 90-120 ℃, and the time of the in-situ grafting reaction is 2-5 hours.
8. The modified conductive filler prepared by the preparation method of any one of claims 1 to 7 comprises a nano silver wire, an-OH group grafted on the surface of the nano silver wire and a terminal-OCN reactive "anchored" chain structure.
9. A conductive adhesive using the modified conductive filler of claim 8 as a conductive filler.
10. The conductive adhesive according to claim 9, wherein each component comprises, in parts by mass: 100 parts of cyanate ester monomer, 5-15 parts of toughening modifier, 18-50 parts of modified conductive filler, 0.01-0.05 part of functional assistant, 0.5-2 parts of thickener, 0.1-0.5 part of defoamer and 30-110 parts of solvent.
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| CN111440562B (en) | 2021-03-30 |
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Effective date of registration: 20220608 Address after: 528400 zone a, floor 3, plant building 91, Gaoping Avenue, Gaoping Industrial Zone, Sanjiao Town, Zhongshan City, Guangdong Province Patentee after: Guangdong Hongqi New Material Co.,Ltd. Address before: 528402, Xueyuan Road, 1, Shiqi District, Guangdong, Zhongshan Patentee before: University OF ELECTRONIC SCIENCE AND TECHNOLOGY OF CHINA, ZHONGSHAN INSTITUTE |