CN115058203A - Formula and preparation method of micro-nano hybrid thermosetting conductive adhesive film - Google Patents

Formula and preparation method of micro-nano hybrid thermosetting conductive adhesive film Download PDF

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Publication number
CN115058203A
CN115058203A CN202210892795.6A CN202210892795A CN115058203A CN 115058203 A CN115058203 A CN 115058203A CN 202210892795 A CN202210892795 A CN 202210892795A CN 115058203 A CN115058203 A CN 115058203A
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micro
nano
adhesive film
particles
conductive
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王浩
钱力
应海峰
魏彬彬
徐凯华
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Changzhou Hongju Electronic Technology Co ltd
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Changzhou Hongju Electronic Technology 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
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/10—Adhesives in the form of films or foils without carriers
    • 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
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/08—Macromolecular additives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • 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
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • 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
    • 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
    • C08K2003/085—Copper
    • 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
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets
    • C08L2203/206—Applications use in electrical or conductive gadgets use in coating or encapsulating of electronic parts
    • 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
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
    • 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
    • C09J2423/00—Presence of polyolefin
    • C09J2423/04—Presence of homo or copolymers of ethene
    • C09J2423/045—Presence of homo or copolymers of ethene in the release coating
    • 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
    • C09J2467/00—Presence of polyester
    • C09J2467/005—Presence of polyester in the release coating

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Conductive Materials (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

The invention discloses a formula of a micro-nano hybrid thermosetting conductive adhesive film, which comprises the following components in parts by weight: epoxy resin, epoxy modifier, conductive particles, antioxidant, curing agent, dispersant and diluent. The preparation method comprises the following steps: firstly, adding the raw material components into a reaction kettle for reaction; secondly, the conductive paste obtained in the step I is conveyed to a coating workshop to be coated on a release film, and the temperature of a coating channel is set to 70 ℃, 90 ℃ and 115 ℃ respectively from beginning to end; the coating speed is controlled to be 8-12 m/min. The technical scheme is characterized in that a conductive network in the existing conductive adhesive film system is optimized by introducing nano-scale copper powder, and the seepage threshold value and the raw material cost are reduced by filling nano-scale particles; meanwhile, the resin matrix is optimized, so that the water absorption of the resin is greatly reduced, and higher stripping force can be continuously provided; provides a novel low-resistance and high-stripping-force thermosetting conductive adhesive film.

Description

Formula and preparation method of micro-nano hybrid thermosetting conductive adhesive film
Technical Field
The invention relates to the field of functional polymer composite materials, in particular to a formula and a preparation method of a micro-nano hybrid thermosetting conductive adhesive film.
Background
Since the 90 s of the 20 th century, electronic science and technology has been developed vigorously, products are gradually miniaturized, miniaturized and highly integrated, and the Sn-Pb welding mode adopted by the traditional electronic packaging is not enough to meet the current production requirements from the aspects of reliability and environmental protection. Compared with tin-lead solder, the conductive adhesive has the following advantages: the bonding temperature is low (100-; the connecting capacity of high density and narrow spacing is realized; has good environmental protection performance; can be connected with different substrates; the bonding equipment is simple and low in cost. In addition, the conductive adhesive can be suitable for connection of a flexible circuit board, and has great development prospect and market demand.
The ICA isotropic conductive adhesive mainly comprises a resin matrix and a conductive filler. Wherein the resin matrix provides a mechanical skeleton and determines the mechanical property and the bonding performance of the colloid; the conductive particles with different types and shapes determine the conductivity. The resin matrix can be divided into thermoplastic resin and thermosetting resin, the thermoplastic resin usually has few branched chains, the stability of the structure is difficult to maintain after being heated, and the charged particles can be displaced under high-temperature operation, so that the resistance value is changed violently. Thermosetting resins usually have reactive groups and can be cured into a stable three-dimensional network structure, so that charged particles are uniformly distributed and contact resistance is stable. Therefore, epoxy resin, acrylic resin, phenolic resin, etc. are widely used as matrix materials in practical applications.
However, the epoxy-based conductive adhesives in the market all face an unavoidable problem: the high water absorption caused by free hydroxyl after epoxy curing enables the epoxy resin to have obvious electric contact resistance change in a damp and hot environment, so that accidents are easily caused, and the large-scale application of the epoxy resin is blocked; in the preparation methods of the epoxy conductive adhesive films disclosed in patent numbers (CN 104673111B) and (CN 104017511B), the water absorption rate is not characterized, and the method is not universal;
the patent number (CN 105838311B) discloses a polyurethane modified epoxy conductive adhesive film, but the water absorption rate is 0.2%, which only meets the actual implementation standard of the electronic industry, and needs to be improved. In addition, the current high-end conductive adhesive has expensive filler cost and single conductive particle; however, the performances of the current partially commercialized conductive adhesive films are relatively general, and only one of the conductive adhesive films can be optimized in the optimization of the stripping force and the conductivity, and a reasonable symbiotic scheme is not provided.
In view of the above problems, it is necessary to develop a novel low-cost conductive adhesive film with extremely low resistivity and moisture absorption on the premise of high peeling force.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a preparation method of a low-cost high-performance thermosetting conductive adhesive film, nanometer copper powder is introduced into gaps of a conductive network of traditional micron-sized charged particles to obtain a more compact high-density conductive network, and the introduction of the nanometer copper powder also greatly reduces the cost while reducing the percolation threshold.
The technical purpose of the invention is realized by the following technical scheme:
the invention discloses a formula and a preparation method of a micro-nano hybrid thermosetting conductive adhesive film, wherein the formula of the micro-nano hybrid thermosetting conductive adhesive film in a preferred embodiment of the invention comprises the following components of epoxy resin, an epoxy resin modifier, conductive particles (a micro-nano blending system), a curing agent, an antioxidant, a dispersing agent and a diluting agent.
The conductive adhesive layer is prepared from the following raw materials: 50-70 parts of epoxy resin, 30-50 parts of epoxy modifier, 35-55 parts of conductive particles, 0.05-0.2 part of antioxidant, 0.25-0.65 part of curing agent, 0.1-0.3 part of dispersant and 5-15 parts of diluent (by weight).
Further, the epoxy modifier comprises one or a mixture of several of organic silicon resin, polyurethane, phenolic resin and polyimide resin.
Further, the micron-sized conductive particles comprise one or a mixture of silver-coated copper, silver-coated silicon dioxide particles and silver-coated polystyrene particles.
Furthermore, the morphology of the conductive particles comprises one or a mixture of several of rod shape, spherical shape and sheet shape.
Further, the curing agent comprises one or a mixture of polyamines, acid anhydrides and imidazoles.
Further, the antioxidant comprises one or a mixture of several of antioxidant 264, antioxidant 1076 and antioxidant P-EBQ.
Further, the dispersing agent is one or a mixture of Glide 410, Crainen PTS and Efka-4666.
Furthermore, the diluent is one or a mixture of a plurality of benzene solvents, alcohol solvents, ester solvents and ketone solvents.
The invention provides a micro-nano blending method of the conductive particles, which comprises the following steps:
carrying out ultrasonic washing on nano copper powder particles by using a mixed solution of hydrochloric acid and 75% ethanol, washing the nano copper powder particles for a plurality of times by using sufficient absolute ethyl alcohol after washing is finished, filtering the washed nano copper powder particles for standby use, then mixing the absolute ethyl alcohol, the active coupling agent and the short-chain organic acid according to a certain volume ratio, adding the mixture into the treated copper powder, and carrying out ultrasonic stirring for 2-5 hours at the temperature of 60-80 ℃; distilling off the excessive liquid phase by using a rotary evaporator after the reaction is finished, and drying the liquid phase in a drying box under the atmosphere of N2 for 4 hours after the liquid phase is drained out;
II, mixing the nano copper powder (A) and the micron-sized silver-plated particles (B) according to a certain weight ratio, and then mixing in a planetary ball mill for 0.5-2 h at the rotating speed of 350r/min to obtain uniformly dispersed micro-nano mixed conductive particles (C);
further, the surfactant comprises one or a mixture of more of Dow Corning OFS-6341, KBM503 and KH 560.
Further, the particle diameter of the nano-scale conductive particles (A) is 50-100 nm.
Further, the particle size of the micron-sized conductive particles (B) is 10-50 um.
Further, the weight ratio of the conductive particles (a) to the conductive particles (B) in the micro-nano mixed conductive particles (C) is 1: 3-1: 6.
further, the volume ratio of the absolute ethyl alcohol, the coupling agent and the organic acid is 10: 0.5: 3-10: 0.5: 6.
further, the organic acid is one or a mixture of more of oxalic acid, adipic acid and terephthalic acid.
A preparation method of a micro-nano hybrid thermosetting conductive adhesive film comprises the following steps:
adding epoxy resin, epoxy modifier resin, a curing agent, a dispersing agent and a diluting agent into a reaction kettle, reacting for 2-4 hours at 60-80 ℃ under 2Mpa, and then sequentially adding conductive particles A, B and C in batches, wherein the weight ratio of the conductive particles A, B and C is as follows: 1:1: 0.5-1: 1:2, wherein the interval time is 30min each time, then adding a metal antioxidant, and continuously stirring for 2h to finish the reaction;
secondly, the conductive paste obtained in the step I is conveyed to a coating workshop for coating operation, and the temperature of a coating channel is set to 70 ℃, 90 ℃ and 115 ℃ respectively from beginning to end; the coating speed is controlled to be 8-12 m/min.
Further, the thickness of the adhesive film is 40 um-100 um, and the adhesive film is customized according to customer requirements.
Furthermore, the release film layer is a transparent release PET film or a white PE release film
In conclusion, the invention has the following beneficial effects:
the conductive network in the existing conductive adhesive film system is optimized by introducing the nano-copper powder, and the seepage threshold and the raw material cost are reduced by filling nano-sized particles; meanwhile, the resin matrix is optimized, so that the water absorption of the resin is greatly reduced, and higher stripping force can be continuously provided; provides a novel low-resistance and high-stripping-force thermosetting conductive adhesive film.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. 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.
The formula of the micro-nano hybrid thermosetting conductive adhesive film in the preferred embodiment of the invention comprises the components of epoxy resin, an epoxy resin modifier, conductive particles (a micro-nano blending system), a curing agent, an antioxidant, a dispersing agent and a diluting agent.
The conductive adhesive layer is prepared from the following raw materials: 50-70 parts of epoxy resin, 30-50 parts of epoxy modifier, 35-55 parts of conductive particles, 0.05-0.2 part of antioxidant, 0.25-0.65 part of curing agent, 0.1-0.3 part of dispersant and 5-15 parts of diluent (by weight).
The epoxy modifier comprises one or a mixture of more of organic silicon resin, polyurethane, phenolic resin and polyimide resin.
The micron-sized conductive particles comprise one or a mixture of silver-coated copper, silver-coated silicon dioxide particles and silver-coated polystyrene particles.
The morphology of the conductive particles comprises one or a mixture of several of rod type, spherical type and sheet type.
The curing agent comprises one or a mixture of polyamines, acid anhydrides and imidazoles.
The antioxidant comprises one or more of antioxidant 264, antioxidant 1076 and antioxidant P-EBQ.
The dispersing agent is one or a mixture of Glide 410, Crainen PTS and Efka-4666.
The diluent is one or a mixture of benzene, alcohol, ester and ketone solvents.
The invention provides a micro-nano blending method of the conductive particles, which comprises the following steps:
carrying out ultrasonic washing on copper nanoparticle particles by using a mixed solution of hydrochloric acid and 75% ethanol, washing the copper nanoparticle particles for a plurality of times by using sufficient absolute ethyl alcohol after washing, filtering the copper nanoparticle particles for later use, then mixing the absolute ethyl alcohol, the active coupling agent and the short-chain organic acid according to a certain volume ratio, adding the mixture into the treated copper powder, and carrying out ultrasonic stirring for 2-5 hours at the temperature of 60-80 ℃; distilling off the excessive liquid phase by using a rotary evaporator after the reaction is finished, and drying the liquid phase in a drying box under the atmosphere of N2 for 4 hours after the liquid phase is drained out;
II, mixing the nano copper powder (A) and the micron-sized silver-plated particles (B) according to a certain weight ratio, and then mixing in a planetary ball mill for 0.5-2 h at the rotating speed of 350r/min to obtain uniformly dispersed micro-nano mixed conductive particles (C);
the surfactant comprises one or more of Dow Corning OFS-6341, KBM503 and KH 560.
The particle diameter of the nano-scale conductive particles (A) is 50-100 nm.
The particle size of the micron-sized conductive particles (B) is 10-50 um.
The weight ratio of the conductive particles (A) to the conductive particles (B) in the micro-nano mixed conductive particles (C) is 1: 3-1: 6.
the volume ratio of the absolute ethyl alcohol, the coupling agent and the organic acid is 10: 0.5: 3-10: 0.5: 6.
the organic acid is one or a mixture of more of oxalic acid, adipic acid and terephthalic acid.
A preparation method of a micro-nano hybrid thermosetting conductive adhesive film comprises the following steps:
adding epoxy resin, epoxy modifier resin, a curing agent, a dispersing agent and a diluting agent into a reaction kettle, reacting for 2-4 hours at 60-80 ℃ under 2Mpa, and then sequentially adding conductive particles A, B and C in batches, wherein the weight ratio of the conductive particles A, B and C is as follows: 1:1: 0.5-1: 1:2, wherein the interval time is 30min each time, then adding a metal antioxidant, and continuously stirring for 2h to finish the reaction;
secondly, the conductive paste obtained in the step I is conveyed to a coating workshop for coating operation, and the temperature of a coating channel is set to 70 ℃, 90 ℃ and 115 ℃ respectively from beginning to end; the coating speed is controlled to be 8-12 m/min.
The thickness of the adhesive film is 40 um-100 um, and the adhesive film is customized according to customer requirements.
The release film layer is a transparent release PET film or a white PE release film.
Example 1
Placing epoxy resin and polyurethane resin into a reaction kettle, stirring and reacting for 1h at 60 ℃, then adding a curing agent, a dispersing agent and a diluting agent, pressurizing to 2Mpa, continuing to react for 2h, then adding conductive particles A, B, C in sequence at intervals of 30min, finally adding an antioxidant, stirring for 2h, and ending the reaction.
The epoxy resin coating comprises, by weight, 50 parts of epoxy resin, 50 parts of polyurethane resin, 0.25 part of a curing agent, 0.05 part of an antioxidant, 0.1 part of a dispersant and 8 parts of a diluent.
The weight ratio of the conductive particles A, B and C is as follows: 1:1: 0.5.
the particle diameter of the nano-scale conductive particles (A) is 50 nm.
The particle diameter of the micron-sized conductive particles (B) is 10 um.
The weight ratio of the conductive particles (A) to the conductive particles (B) in the micro-nano mixed conductive particles (C) is 1: 3.
example 2
Placing epoxy resin and organic silicon resin into a reaction kettle, stirring and reacting for 1h at 70 ℃, then adding a curing agent, a dispersing agent and a diluent, pressurizing to 2Mpa, continuing to react for 2h, then adding conductive particles A, B, C in sequence at intervals of 30min, finally adding an antioxidant, stirring for 2h, and finishing the reaction.
The epoxy resin coating comprises, by weight, 60 parts of epoxy resin, 40 parts of organic silicon resin, 0.5 part of a curing agent, 0.1 part of an antioxidant, 0.15 part of a dispersant and 10 parts of a diluent.
The weight ratio of the conductive particles A, B and C is as follows: 1:1: 1.
the particle diameter of the nano-scale conductive particles (A) is 65 nm.
The particle diameter of the micron-sized conductive particles (B) is 25 um.
The weight ratio of the conductive particles (A) to the conductive particles (B) in the micro-nano mixed conductive particles (C) is 1: 4.
example 3
Placing epoxy resin and polyimide resin into a reaction kettle, stirring and reacting for 1h at the temperature of 80 ℃, then adding a curing agent, a dispersing agent and a diluent, pressurizing to 2Mpa, continuing to react for 2h, then adding conductive particles A, B, C in sequence at intervals of 30min, finally adding an antioxidant, stirring for 2h, and finishing the reaction.
Wherein, the epoxy resin accounts for 70 parts, the polyimide resin accounts for 30 parts, the curing agent accounts for 0.35 part, the antioxidant accounts for 0.1 part, the dispersant accounts for 0.1 part, and the diluent accounts for 8 parts.
The weight ratio of the conductive particles A, B and C is as follows: 1:1: 1.5.
the particle diameter of the nano-scale conductive particles (A) is 50 nm.
The particle diameter of the micron-sized conductive particles (B) is 50 um.
The weight ratio of the conductive particles (A) to the conductive particles (B) in the micro-nano mixed conductive particles (C) is 1: 5.
in summary, the following steps: the conductive network in the existing conductive adhesive film system is optimized by introducing the nano-copper powder, and the seepage threshold and the raw material cost are reduced by filling nano-sized particles; meanwhile, the resin matrix is optimized, so that the water absorption of the resin is greatly reduced, and higher stripping force can be continuously provided; provides a novel low-resistance and high-stripping-force thermosetting conductive adhesive film.
The foregoing shows and describes the general principles and broad features of the present invention and advantages thereof. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.

Claims (10)

1. A formula of a micro-nano hybrid thermosetting conductive adhesive film is characterized in that: the paint comprises the following components in parts by weight: 50-70 parts of epoxy resin, 30-50 parts of epoxy modifier, 35-55 parts of conductive particles, 0.05-0.2 part of antioxidant, 0.25-0.65 part of curing agent, 0.1-0.3 part of dispersant and 5-15 parts of diluent.
2. The formulation of the micro-nano hybrid thermosetting conductive adhesive film according to claim 1, wherein: the epoxy modifier comprises one or a mixture of more of organic silicon resin, polyurethane, phenolic resin and polyimide resin,
the antioxidant comprises one or more of antioxidant 264, antioxidant 1076 and antioxidant P-EBQ,
the curing agent comprises one or a mixture of polyamines, acid anhydrides and imidazoles,
the dispersant is one or a mixture of more of Glide 410, Crainen PTS and Efka-4666,
the diluent is one or a mixture of benzene, alcohol, ester and ketone solvents.
3. The formula of the micro-nano hybrid thermosetting conductive adhesive film according to claim 1, wherein the micro-nano hybrid thermosetting conductive adhesive film comprises: the conductive particles comprise one or a mixture of more of silver-coated copper, silver-coated silicon dioxide particles and silver-coated polystyrene particles, and the morphology of the conductive particles comprises any one or a mixture of more of rod-shaped, spherical and flaky shapes.
4. The micro-nano blending method of conductive particles according to claim 1, characterized in that: comprises the following steps:
carrying out ultrasonic washing on copper nanoparticle particles by using a mixed solution of hydrochloric acid and 75% ethanol, washing the copper nanoparticle particles for a plurality of times by using sufficient absolute ethanol after washing, filtering the copper nanoparticle particles for standby use, then mixing the absolute ethanol, an active coupling agent and short-chain organic acid according to a certain volume ratio, adding the mixture into the treated copper powder, carrying out ultrasonic stirring at the temperature of 60-80 ℃ for 2-5 h, distilling off redundant liquid phase by using a rotary evaporator after finishing, and placing the liquid phase in a drying box under the atmosphere of N2 for drying for 4h after the liquid phase is discharged;
and II, mixing the nano copper powder (A) and the micron-sized particles (B) according to a certain weight ratio, and then mixing in a planetary ball mill for 0.5-2 h at the rotating speed of 350r/min to obtain uniformly dispersed micro-nano mixed conductive particles (C).
5. The micro-nano blending method of conductive particles according to claim 4, characterized in that: the surfactant comprises one or more of Dow Corning OFS-6341, KBM503 and KH560,
the particle size of nanometer electrically conductive granule (A) is 50~100nm, the particle size of micron order electrically conductive granule (B) is 10~50um, the weight ratio of electrically conductive particle (A) and electrically conductive particle (B) is 1 in the micro-nano mixed electrically conductive particle (C): 3-1: 6.
6. the micro-nano blending method of conductive particles according to claim 4, characterized in that: the absolute ethyl alcohol: coupling agent: the volume ratio of the organic acid is 10: 0.5: 3-10: 0.5: and 6, the organic acid is one or a mixture of more of oxalic acid, adipic acid and terephthalic acid.
7. A preparation method of a micro-nano hybrid thermosetting conductive adhesive film is characterized by comprising the following steps: the method comprises the following steps:
firstly, adding epoxy resin, epoxy modifier resin, a curing agent, a dispersing agent and a diluting agent into a reaction kettle, reacting for 2-4 hours at 60-80 ℃ under 2Mpa, then sequentially adding conductive particles A, B and C in batches with the interval time of 30min each time, then adding a metal antioxidant, continuously stirring for 2 hours, and finishing the reaction;
secondly, the conductive paste obtained in the step I is conveyed to a coating workshop to be coated on a release film, and the temperature of a coating channel is set to 70 ℃, 90 ℃ and 115 ℃ respectively from beginning to end; the coating speed is controlled to be 8-12 m/min.
8. The method for preparing the micro-nano hybrid thermosetting conductive adhesive film according to claim 7, wherein the method comprises the following steps: the weight ratio of the conductive particles A, B and C is as follows: 1:1: 0.5-1: 1: 2.
9. The method for preparing the micro-nano hybrid thermosetting conductive adhesive film according to claim 7, wherein the method comprises the following steps: the thickness of the adhesive film is 40-100 um.
10. The method for preparing the micro-nano hybrid thermosetting conductive adhesive film according to claim 7, wherein the method comprises the following steps: the release film layer is a transparent PET release film or a white PE release film.
CN202210892795.6A 2022-07-27 2022-07-27 Formula and preparation method of micro-nano hybrid thermosetting conductive adhesive film Pending CN115058203A (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103468159A (en) * 2013-03-11 2013-12-25 苏州牛剑新材料有限公司 Silver coated nickel powder conductive adhesive and preparation method thereof
CN103666319A (en) * 2013-12-11 2014-03-26 青岛海洋新材料科技有限公司 Marine climate resistant epoxy conductive adhesive composition
CN103834322A (en) * 2014-03-04 2014-06-04 华进半导体封装先导技术研发中心有限公司 Conductive adhesive and preparation method thereof
CN107987747A (en) * 2017-12-22 2018-05-04 有研粉末新材料（北京）有限公司 A kind of preparation method of nanometer of silver-coated copper powder collaboration flake silver powder conducting resinl
CN110556216A (en) * 2019-09-06 2019-12-10 常州斯威克光伏新材料有限公司 Preparation method of conductive adhesive film

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103468159A (en) * 2013-03-11 2013-12-25 苏州牛剑新材料有限公司 Silver coated nickel powder conductive adhesive and preparation method thereof
CN103666319A (en) * 2013-12-11 2014-03-26 青岛海洋新材料科技有限公司 Marine climate resistant epoxy conductive adhesive composition
CN103834322A (en) * 2014-03-04 2014-06-04 华进半导体封装先导技术研发中心有限公司 Conductive adhesive and preparation method thereof
CN107987747A (en) * 2017-12-22 2018-05-04 有研粉末新材料（北京）有限公司 A kind of preparation method of nanometer of silver-coated copper powder collaboration flake silver powder conducting resinl
CN110556216A (en) * 2019-09-06 2019-12-10 常州斯威克光伏新材料有限公司 Preparation method of conductive adhesive film

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