CN115011279B - Conductive adhesive film material with dual curing mode and preparation method thereof - Google Patents
Conductive adhesive film material with dual curing mode and preparation method thereof Download PDFInfo
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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
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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
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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
- C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
- C09J4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00
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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
- C09J7/00—Adhesives in the form of films or foils
- C09J7/10—Adhesives in the form of films or foils without carriers
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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
- 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
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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
- 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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Abstract
The invention discloses a conductive adhesive film material with a dual curing mode and a preparation method thereof, and belongs to the technical field of conductive adhesive film material preparation. The conductive adhesive film is prepared from the following raw materials in percentage by mass: 25-45% of epoxy resin, 20-40% of triethylene glycol dimethacrylate, 15-30% of conductive particles, 3-5% of thermosetting agent, 0.5-1% of photoinitiator, 0.5-1% of rheological agent, 0.3-1% of diluent, 0.3-1% of cross-linking agent and 0.2-0.5% of silane coupling agent. The conductive adhesive film provided by the invention is prepared from specific conductive particles, and has the advantages of good anisotropism (large insulation resistance), good conductivity (small contact resistance), high peeling strength, good thermal aging resistance and easy storage; and the preparation process is simple, the controllability is strong, and the application prospect is wide.
Description
Technical Field
The invention belongs to the technical field of conductive adhesive film material preparation, and particularly relates to a conductive adhesive film material with a dual curing mode and a preparation method thereof.
Background
The development of microelectronic technology drives the development of microelectronic packaging technology, and has both electricity and heat. Flip chips with excellent characteristics such as mechanical bonding have become the dominant packaging technology. Lead-tin alloy is widely applied as a packaging material in the electronic industry due to the advantages of low cost, good physical property and the like, but has obvious disadvantages: is toxic. Consequently, lead-free alloy packaging materials have been developed, but the disadvantages of high cost, high welding temperature, etc. have greatly limited their application. New adhesive interconnection techniques have been developed and gradually replace traditional soldering techniques; according to different types of adhesives, the adhesive can be divided into various conductive adhesive films, isotropic conductive adhesive films and non-conductive adhesives; the various conductive adhesive films (ACA) have the characteristics of low content of conductive particles, conductive connectors in the vertical direction only and insulating in the water body direction.
According to the form, ACA can be divided into paste and film (ACF), and ACF gradually attracts attention for research and development by virtue of the advantages of environmental protection, narrower connectable distance, low working temperature and the like. Generally, ACF is made of a resin adhesive, conductive particles and related auxiliaries, wherein the conductive particles undergo a development stage in which the original carbon fibers are gradually replaced by lead-free solder and metal microspheres, and many conductive particles are studied and compared at present to directly coat a metal conductive layer on polymer microspheres, as in patent document CN102176337B, CN104480455B and the like; the resin adhesive can be mainly divided into thermoplastic resin and thermal soliton resin, a three-dimensional cross-linked structure can be formed after thermosetting resin is cured, the bonding reliability is high, the contact resistance is low, and therefore more resins are used, and the currently commonly used resins are epoxy resin type resins.
Along with the integration, multi-lead and high performance development of electronic components such as circuit board terminals and IC chips, ACFs with single curing mode cannot meet the requirement of high bonding strength, so conductive adhesive films with dual curing modes are gradually researched and developed. In the prior art, patent document CN111100562B provides a dual-curing anisotropic conductive adhesive film, in which organic matters are pre-dispersed and subjected to magnetic treatment and UV curing, and the treatment method is relatively complex; patent document CN103194166B provides a photo-thermal dual-curing conductive adhesive, which provides a prepolymer epoxy acrylate prepared by a specific method, and the process is still relatively complex. In the prior art, the performance of the conductive adhesive film is still to be further improved.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention aims at providing a conductive adhesive film material with a dual curing mode and a preparation method thereof, wherein specific conductive particles are selected to prepare a conductive adhesive film, and the prepared conductive adhesive film has good anisotropism (large insulation resistance), good conductivity (small contact resistance), high peel strength, good thermal aging resistance and easy storage; and the preparation process is simple and has strong controllability.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
the conductive adhesive film material with the dual curing mode is prepared from the following raw materials in percentage by mass: 25-45% of epoxy resin, 20-40% of triethylene glycol dimethacrylate, 15-30% of conductive particles, 3-5% of thermosetting agent, 0.5-1% of photoinitiator, 0.5-1% of rheological agent, 0.3-1% of diluent, 0.3-1% of cross-linking agent and 0.2-0.5% of silane coupling agent;
wherein the preparation of the conductive particles comprises the following steps:
(1) Preparing polystyrene microspheres for later use;
(2) Adding the polystyrene microsphere obtained in the step (1) into water, and performing ultrasonic dispersion to obtain a solution a; adding chitosan into acetic acid solution, and stirring uniformly to obtain solution b; then adding the solution a into the solution b, and stirring and reacting for 3-5 h at 25-40 ℃; after the stirring reaction is finished, the product c is obtained through centrifugal treatment;
(3) Dissolving the product c obtained in the step (2) in water, then adding glutaraldehyde solution, and stirring for reacting for 12-36 h; after the stirring reaction is finished, the product d is obtained through centrifugation and drying treatment;
(4) Mixing the plating solution with the product d obtained in the step (3), reacting for 0.5-2 h under the stirring condition, and performing centrifugation, washing and drying treatment to obtain the conductive particles.
As a further preferable mode of the technical scheme of the invention, in the step (2), the microsphere concentration of the solution a is 2-5 mg/mL; the concentration of chitosan in the solution b is 4-10 mg/mL, and the concentration of acetic acid solution is 3-7%wt; the volume and dosage ratio of the solution a to the solution b is 10:1-3.
As a further preferable mode of the technical scheme of the invention, in the step (3), the volume and the dosage ratio of glutaraldehyde solution to solution a is 10:0.4-0.8, and the concentration of glutaraldehyde solution is 50-60%wt.
As a further preferred embodiment of the present invention, in the step (4), the ratio of the plating solution to the product d is 1L: 6-9 g; the plating solution comprises the following components: 13g/L copper sulfate, 1.1g/L sodium dimercaptopropane sulfonate, 14g/L potassium sodium tartrate, 25mL/L disodium ethylenediamine tetraacetate, 22mL/L formaldehyde.
As a further preferred embodiment of the present invention, the epoxy resin is 3, 4-epoxycyclohexylformate.
As a further preferred embodiment of the present invention, the thermosetting agent is 2-ethyl-4-methylimidazole; the photoinitiator is benzil dimethyl ether; the diluent is propylene oxide; the cross-linking agent is glycidyl methacrylate; the coupling agent is KH-570.
As a further preferred embodiment of the present invention, the rheological agent is modified bentonite.
As a further preferred embodiment of the present invention, the modified bentonite has the brand HFGEL-170.
Meanwhile, the invention discloses a preparation method of the conductive adhesive film material, which comprises the following steps:
s1, adding a thermosetting agent into triethylene glycol dimethacrylate, and uniformly stirring; then adding epoxy resin, conductive particles, a photoinitiator, a rheological agent, a diluent, a cross-linking agent and a silane coupling agent, and uniformly stirring under the condition of low temperature and light shielding to obtain conductive adhesive;
s2, the conductive adhesive obtained in the step S1 is firstly subjected to rotary coating, and then ultraviolet curing treatment is carried out, so that the conductive adhesive film with a dual curing mode is obtained.
As a further preferred aspect of the present invention, the conditions for uv curing are: the power is 900W, the temperature is 150 ℃, and the curing time is 30-60 s.
Compared with the prior art, the invention has the following beneficial effects:
(1) The conductive adhesive film material in the dual-curing mode provided by the invention takes triethylene glycol dimethacrylate and 3, 4-epoxy cyclohexyl formate as main resin matrixes, and the excellent performances of small contact resistance and high peeling strength of the conductive adhesive film material are realized by matching with specific conductive particles, so that the conductive adhesive film material is a dual-curing conductive adhesive film with photo-curing and thermal curing functions and wider application prospects.
(2) According to the conductive adhesive film material with the dual curing mode, polymers are often adopted to coat a metal conductive layer in the prior art of conductive particles, pretreatment processes such as coarsening, sensitization, activation and the like are often needed, pollution is large, and a treatment mode is complex; the invention creatively takes common polystyrene microspheres as a main raw material, firstly loads chitosan, and then reduces loaded copper simple substance; the chitosan is a common polymer compound, contains rich amino, hydroxyl and other functional groups, takes polystyrene microspheres as cores, can fully crosslink and graft the chitosan, and can efficiently complex copper ions through rich sites of the chitosan, reduce the copper ions into copper simple substances by utilizing the amino on the surface of the chitosan, promote the surface growth of the copper simple substances and obtain the conductive particles of the copper-containing layer. In fact, polystyrene grafted chitosan is often used for adsorbing heavy metals in the prior art, so the conception is novel and unique, and the effect of the polystyrene grafted chitosan applied to the conductive adhesive film is good.
(3) According to the conductive adhesive film material with the dual curing mode, the leveling agent does not adopt silicon dioxide commonly used in the prior art, but adopts the bentonite modified by music, so that the defect that the silicon dioxide is easy to agglomerate can be avoided, the dispersibility is good, the stability and the coating property of adhesive film preparation can be greatly improved, and the quality of a coating film is improved.
(4) The preparation method of the conductive adhesive film material in the dual curing mode provided by the invention has the advantages of simple process, strong controllability and lower preparation cost.
Detailed Description
The following description of the embodiments of the present invention will clearly and fully describe the technical aspects of the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the present invention without making any inventive effort, are intended to fall within the scope of the present invention.
It should be noted that all the raw materials in the present invention are purchased from the market unless otherwise specified; wherein the brand of the modified bentonite is HFGEL-170.
Example 1
The conductive adhesive film material with the dual curing mode is prepared from the following raw materials in percentage by mass of 100% of the total: 40% of epoxy resin, 32% of triethylene glycol dimethacrylate, 22% of conductive particles, 4% of a thermosetting agent, 0.6% of a photoinitiator, 0.4% of a rheological agent, 0.4% of a diluent, 0.3% of a crosslinking agent and 0.3% of a silane coupling agent;
wherein the preparation of the conductive particles comprises the following steps:
(1) Preparing polystyrene microspheres for later use; the preparation of the polystyrene microsphere comprises the following steps: under the protection of nitrogen and under the stirring condition, adding 5g of styrene monomer into 100mL of water, then adding 0.11g of potassium persulfate, and stirring and reacting for 18h at 65 ℃; after the reaction is completed, the polystyrene microsphere is obtained;
(2) Adding the polystyrene microsphere obtained in the step (1) into water according to the concentration of 3mg/mL, and performing ultrasonic dispersion to obtain a solution a; adding chitosan into acetic acid solution with the weight of 4.5 percent according to the concentration of 6.5mg/mL, and uniformly stirring to obtain solution b; subsequently, 40mL of solution a was added to 12mL of solution b, and the mixture was stirred at 32℃for 3.5 hours; after the stirring reaction is finished, the product c is obtained through centrifugal treatment;
(3) Dissolving all the product c obtained in the step (2) in water, then adding 2mL of 55%wt glutaraldehyde solution, and stirring for reaction for 18h; after the stirring reaction is finished, the product d is obtained through centrifugation and drying treatment;
(4) According to the dosage ratio of 1L:7g, mixing the plating solution with the product d obtained in the step (3), reacting for 1h under the stirring condition, and carrying out centrifugation, washing and drying treatment to obtain the conductive particles.
Wherein, the plating solution comprises the following components: 13g/L copper sulfate, 1.1g/L sodium dimercaptopropane sulfonate, 14g/L potassium sodium tartrate, 25mL/L disodium ethylenediamine tetraacetate, 22mL/L formaldehyde.
Wherein the epoxy resin is 3, 4-epoxycyclohexyl formate.
Wherein the thermosetting agent is 2-ethyl-4-methylimidazole; the photoinitiator is benzil dimethyl ether; the diluent is propylene oxide; the cross-linking agent is glycidyl methacrylate; the coupling agent is KH-570; the rheological agent is modified bentonite.
In this embodiment, a method for preparing the conductive adhesive film material is also provided, including the following steps:
s1, adding a thermosetting agent into triethylene glycol dimethacrylate, and uniformly stirring; then adding epoxy resin, conductive particles, a photoinitiator, a rheological agent, a diluent, a cross-linking agent and a silane coupling agent, and uniformly stirring under the condition of low temperature and light shielding to obtain conductive adhesive;
s2, the conductive adhesive obtained in the step S1 is firstly subjected to rotary coating, and then ultraviolet curing treatment is carried out, so that the conductive adhesive film with a dual curing mode is obtained.
Wherein, the ultraviolet curing conditions are as follows: the power is 900W, the temperature is 150 ℃, and the curing time is 30s.
Example 2
The conductive adhesive film material with the dual curing mode is prepared from the following raw materials in percentage by mass of 100% of the total: 40% of epoxy resin, 34% of triethylene glycol dimethacrylate, 20% of conductive particles, 4.1% of thermosetting agent, 0.5% of photoinitiator, 0.3% of rheological agent, 0.3% of diluent, 0.4% of cross-linking agent and 0.4% of silane coupling agent;
wherein the preparation of the conductive particles comprises the following steps:
(1) Preparing polystyrene microspheres for later use; the preparation of the polystyrene microsphere comprises the following steps: under the protection of nitrogen and under the stirring condition, adding 5g of styrene monomer into 100mL of water, then adding 0.11g of potassium persulfate, and stirring and reacting for 18h at 65 ℃; after the reaction is completed, the polystyrene microsphere is obtained;
(2) Adding the polystyrene microsphere obtained in the step (1) into water according to the concentration of 3.5mg/mL, and performing ultrasonic dispersion to obtain a solution a; adding chitosan into 5%wt acetic acid solution according to the concentration of 6mg/mL, and uniformly stirring to obtain solution b; subsequently, 40mL of the solution a was added to 10mL of the solution b, and the mixture was stirred at 32℃for 4 hours; after the stirring reaction is finished, the product c is obtained through centrifugal treatment;
(3) Dissolving all the product c obtained in the step (2) in water, then adding 2.4mL of 50%wt glutaraldehyde solution, and stirring for reaction for 22h; after the stirring reaction is finished, the product d is obtained through centrifugation and drying treatment;
(4) According to the dosage ratio of 1L:7.5g of plating solution and the product d obtained in the step (3) are mixed and reacted for 1.5h under the stirring condition, and the conductive particles are obtained after centrifugation, washing and drying treatment.
Wherein, the plating solution comprises the following components: 13g/L copper sulfate, 1.1g/L sodium dimercaptopropane sulfonate, 14g/L potassium sodium tartrate, 25mL/L disodium ethylenediamine tetraacetate, 22mL/L formaldehyde.
Wherein the epoxy resin is 3, 4-epoxycyclohexyl formate.
Wherein the thermosetting agent is 2-ethyl-4-methylimidazole; the photoinitiator is benzil dimethyl ether; the diluent is propylene oxide; the cross-linking agent is glycidyl methacrylate; the coupling agent is KH-570; the rheological agent is modified bentonite.
In this embodiment, a method for preparing the conductive adhesive film material is also provided, including the following steps:
s1, adding a thermosetting agent into triethylene glycol dimethacrylate, and uniformly stirring; then adding epoxy resin, conductive particles, a photoinitiator, a rheological agent, a diluent, a cross-linking agent and a silane coupling agent, and uniformly stirring under the condition of low temperature and light shielding to obtain conductive adhesive;
s2, the conductive adhesive obtained in the step S1 is firstly subjected to rotary coating, and then ultraviolet curing treatment is carried out, so that the conductive adhesive film with a dual curing mode is obtained.
Wherein, the ultraviolet curing conditions are as follows: the power is 900W, the temperature is 150 ℃, and the curing time is 35s.
Example 3
The conductive adhesive film material with the dual curing mode is prepared from the following raw materials in percentage by mass of 100% of the total: 39% of epoxy resin, 35% of triethylene glycol dimethacrylate, 20% of conductive particles, 3.8% of thermosetting agent, 0.6% of photoinitiator, 0.3% of rheological agent, 0.3% of diluent, 0.5% of cross-linking agent and 0.5% of silane coupling agent;
wherein the preparation of the conductive particles comprises the following steps:
(1) Preparing polystyrene microspheres for later use; the preparation of the polystyrene microsphere comprises the following steps: under the protection of nitrogen and under the stirring condition, adding 5g of styrene monomer into 100mL of water, then adding 0.11g of potassium persulfate, and stirring and reacting for 18h at 65 ℃; after the reaction is completed, the polystyrene microsphere is obtained;
(2) Adding the polystyrene microsphere obtained in the step (1) into water according to the concentration of 4mg/mL, and performing ultrasonic dispersion to obtain a solution a; adding chitosan into acetic acid solution with the weight of 5 percent according to the concentration of 7mg/mL, and uniformly stirring to obtain solution b; subsequently, 40mL of solution a was added to 8mL of solution b, and the mixture was stirred at 28℃for 5 hours; after the stirring reaction is finished, the product c is obtained through centrifugal treatment;
(3) Dissolving all the product c obtained in the step (2) in water, then adding 2.6mL of 50%wt glutaraldehyde solution, and stirring for reaction for 24 hours; after the stirring reaction is finished, the product d is obtained through centrifugation and drying treatment;
(4) According to the dosage ratio of 1L:8g, mixing the plating solution with the product d obtained in the step (3), reacting for 2h under the stirring condition, and carrying out centrifugation, washing and drying treatment to obtain the conductive particles.
Wherein, the plating solution comprises the following components: 13g/L copper sulfate, 1.1g/L sodium dimercaptopropane sulfonate, 14g/L potassium sodium tartrate, 25mL/L disodium ethylenediamine tetraacetate, 22mL/L formaldehyde.
Wherein the epoxy resin is 3, 4-epoxycyclohexyl formate.
Wherein the thermosetting agent is 2-ethyl-4-methylimidazole; the photoinitiator is benzil dimethyl ether; the diluent is propylene oxide; the cross-linking agent is glycidyl methacrylate; the coupling agent is KH-570; the rheological agent is modified bentonite.
In this embodiment, a method for preparing the conductive adhesive film material is also provided, including the following steps:
s1, adding a thermosetting agent into triethylene glycol dimethacrylate, and uniformly stirring; then adding epoxy resin, conductive particles, a photoinitiator, a rheological agent, a diluent, a cross-linking agent and a silane coupling agent, and uniformly stirring under the condition of low temperature and light shielding to obtain conductive adhesive;
s2, the conductive adhesive obtained in the step S1 is firstly subjected to rotary coating, and then ultraviolet curing treatment is carried out, so that the conductive adhesive film with a dual curing mode is obtained.
Wherein, the ultraviolet curing conditions are as follows: the power is 900W, the temperature is 150 ℃, and the curing time is 40s.
The performance test was performed on the dual-curing-mode conductive adhesive films prepared in examples 1 to 3, and the performance test was specifically as follows:
appearance observation: the conductive adhesive films prepared in examples 1 to 3 have no bubbles in apparent observation, and the film surface is flat and complete.
And (3) testing the performance of the lamination resistor: and (3) hot-pressing the interconnection for 15s at 180 ℃ under the conditions of a pitch of 120 mu m and a line width of 180 mu m and a hot-pressing pressure of 1.6Mpa, and testing the contact resistance value of the interconnection point.
Resistance to thermal ageing: curing the pressed test material (material in the pressed resistance performance test) for 1h at 160 ℃ in an oven, and then soaking the cured test material in a tin furnace at 300 ℃ for 10s for three times; and finally, testing the resistance by using a direct current low-resistance tester, and representing the thermal aging resistance of the conductive adhesive by using the resistance change degree.
Room temperature storage: placing the conductive adhesive films in examples 1-3 in a constant temperature and humidity machine, and storing for 240 hours at 25 ℃ and 50% humidity; after the storage is finished, the conductive adhesive is interconnected by hot pressing for 15 seconds at 180 ℃ under the hot pressing pressure of 1.6Mpa, and the resistance change is tested by a direct current low resistance tester, so that the room temperature storage property of the conductive adhesive is represented by the resistance change degree.
Peel strength test: the test was performed with reference to IPC-TM-650.2.4.9.
And (3) adhesive film thickness test: the test was performed with reference to GB/T7125.
The test results are shown in Table 1.
TABLE 1 resistance Properties, strength and Peel thickness test results
As can be seen from Table 1, the conductive adhesive film prepared by the invention has good anisotropism (large insulation resistance), good conductivity (small contact resistance), high peeling strength, good thermal aging resistance and easy storage.
The technical idea of the present invention is described by the above embodiments, but the present invention is not limited to the above embodiments, that is, it does not mean that the present invention must be implemented depending on the above embodiments. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of individual raw materials for the product of the present invention, addition of auxiliary components, selection of specific modes, etc., falls within the scope of the present invention and the scope of disclosure.
Claims (7)
1. The conductive adhesive film material in the dual curing mode is characterized by being prepared from the following raw materials in percentage by mass: 25-45% of epoxy resin, 20-40% of triethylene glycol dimethacrylate, 15-30% of conductive particles, 3-5% of thermosetting agent, 0.5-1% of photoinitiator, 0.5-1% of rheological agent, 0.3-1% of diluent, 0.3-1% of cross-linking agent and 0.2-0.5% of silane coupling agent; the epoxy resin is 3, 4-epoxy cyclohexyl formate; the rheological agent is modified bentonite;
wherein the preparation of the conductive particles comprises the following steps:
(1) Preparing polystyrene microspheres for later use;
(2) Adding the polystyrene microsphere obtained in the step (1) into water, and performing ultrasonic dispersion to obtain a solution a; adding chitosan into acetic acid solution, and stirring uniformly to obtain solution b; then adding the solution a into the solution b, and stirring and reacting for 3-5 h at 25-40 ℃; after the stirring reaction is finished, the product c is obtained through centrifugal treatment;
(3) Dissolving the product c obtained in the step (2) in water, then adding glutaraldehyde solution, and stirring for reacting for 12-36 h; after the stirring reaction is finished, the product d is obtained through centrifugation and drying treatment;
(4) Mixing the plating solution with the product d obtained in the step (3), reacting for 0.5-2 h under the stirring condition, and performing centrifugation, washing and drying treatment to obtain the conductive particles; the dosage ratio of the plating solution to the product d is 1L: 6-9 g; the plating solution comprises the following components: 13g/L copper sulfate, 1.1g/L sodium dimercaptopropane sulfonate, 14g/L potassium sodium tartrate, 25mL/L disodium ethylenediamine tetraacetate, 22mL/L formaldehyde.
2. The dual-curing-mode conductive adhesive film material according to claim 1, wherein in the step (2), the microsphere concentration of the solution a is 2-5 mg/mL; the concentration of chitosan in the solution b is 4-10 mg/mL, and the concentration of acetic acid solution is 3-7%wt; the volume and dosage ratio of the solution a to the solution b is 10:1-3.
3. The dual curing mode conductive adhesive film material according to claim 1, wherein in the step (3), the volume ratio of glutaraldehyde solution to solution a is 10:0.4-0.8, and the concentration of glutaraldehyde solution is 50-60% wt.
4. The dual-curing-mode conductive adhesive film material according to claim 1, wherein the thermosetting agent is 2-ethyl-4-methylimidazole; the photoinitiator is benzil dimethyl ether; the diluent is propylene oxide; the cross-linking agent is glycidyl methacrylate; the coupling agent is KH-570.
5. The dual curing mode conductive adhesive film material of claim 1, wherein the modified bentonite has a brand of HFGEL-170.
6. A method for preparing the conductive adhesive film material as claimed in any one of claims 1 to 5, comprising the steps of:
s1, adding a thermosetting agent into triethylene glycol dimethacrylate, and uniformly stirring; then adding epoxy resin, conductive particles, a photoinitiator, a rheological agent, a diluent, a cross-linking agent and a silane coupling agent, and uniformly stirring under the condition of low temperature and light shielding to obtain conductive adhesive;
s2, the conductive adhesive obtained in the step S1 is firstly subjected to rotary coating, and then ultraviolet curing treatment is carried out, so that the conductive adhesive film with a dual curing mode is obtained.
7. The method of claim 6, wherein the ultraviolet curing conditions are: the power is 900W, the temperature is 150 ℃, and the curing time is 30-60 s.
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| JP5519938B2 (en) * | 2008-04-01 | 2014-06-11 | Ｄｏｗａエレクトロニクス株式会社 | Method for producing copper powder for conductive paste |
| CN102176337B (en) * | 2011-01-06 | 2013-01-09 | 天津大学 | Composite conductive particles for anisotropic conductive film and preparation method |
| CN102532572B (en) * | 2011-12-29 | 2013-08-14 | 东北大学 | Preparation method of quaternized chitosan anion hybrid membrane doped with positive polystyrene latex |
| CN102634286B (en) * | 2012-05-17 | 2013-08-14 | 深圳市飞世尔实业有限公司 | Method for preparing photo-thermal dual curable type anisotropic conductive film |
| CN111100562B (en) * | 2019-12-20 | 2021-08-17 | 深圳市撒比斯科技有限公司 | Dual-curing anisotropic conductive adhesive film and preparation method thereof |
| CN114073921A (en) * | 2020-08-10 | 2022-02-22 | 深圳先进技术研究院 | Composite microsphere and preparation method and application thereof |
| WO2022032440A1 (en) * | 2020-08-10 | 2022-02-17 | 深圳先进技术研究院 | Composite microsphere, and preparation method therefor and application thereof |
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