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CN-121975321-A - Multifunctional polyimide composite film with layered structure and preparation method thereof

CN121975321ACN 121975321 ACN121975321 ACN 121975321ACN-121975321-A

Abstract

The invention relates to the technical field of electronic packaging materials, in particular to a multifunctional polyimide composite film with a layered structure and a preparation method thereof. The preparation method of the composite film comprises the steps of preparing a polyamic acid solution, adding alloy powder, uniformly mixing and adjusting the solid content, coating the mixed solution on a flat plate, preheating, and performing programmed thermal imidization treatment to finally form the multifunctional polyimide composite film. The method has simple process and low cost, and is suitable for large-scale production, and the prepared polyimide composite film has excellent photo-thermal conversion, electromagnetic shielding and in-plane heat conduction properties.

Inventors

  • ZHANG PING

Assignees

  • 中欧电子材料国际创新中心(合肥)有限公司

Dates

Publication Date
20260505
Application Date
20260313

Claims (10)

  1. 1. A multifunctional polyimide composite film with a layered structure is characterized in that, The composite film is formed by compounding a polyimide matrix and alloy powder; the polyimide matrix at least contains an imide ring structure; The alloy powder is distributed in a certain layer thickness range near one surface of the polyimide composite film to form a layered structure.
  2. 2. The multifunctional polyimide composite membrane with the layered structure according to claim 1, wherein the thickness of the multifunctional polyimide composite membrane is 2 μm-1mm, and the thickness of the membrane layer where the alloy powder is positioned is 5-90% of the total thickness of the composite membrane.
  3. 3. The multifunctional polyimide composite film having a layered structure according to claim 1, wherein the alloy powder contains at least two of nickel, iron, gold, silver, bismuth, aluminum, titanium, magnesium, tin, copper, zinc, cerium, indium, antimony, germanium, calcium, gallium, tellurium, selenium, lead, cobalt, manganese elements, and the particle size of the alloy powder is 200nm to 500 μm.
  4. 4. A method for producing the multifunctional polyimide composite film having a layered structure according to any one of claims 1 to 3, comprising the steps of: s1, preparing a polyamic acid solution, namely dissolving a diamine monomer in an organic solvent, adding a dianhydride monomer under the stirring condition, controlling the molar ratio of the dianhydride monomer to the diamine monomer to be (0.90-1.25): 1, and stirring and reacting for 1-4 hours at room temperature to obtain a polyamic acid solution with the solid content of 10% -25%; s2, preparing a polyamic acid mixed solution, namely mixing and stirring the polyamic acid solution and the alloy powder uniformly, wherein the mixing mass ratio is 100 (0.4-2.4), adding an organic solvent to adjust the solid content of the mixed solution to 18% -22%, and then carrying out defoaming treatment; s3, coating and preheating, namely coating the mixed solution subjected to the defoaming treatment on a flat plate, wherein the coating thickness is 1-1200 mu m, and then placing the flat plate in a 60-90 ℃ oven for preheating for 30-180 minutes; s4, thermal imidization, namely placing the preheated composite film in a high-temperature oven, and performing step heating heat treatment according to the following procedures, namely firstly, keeping at 60-80 ℃ for 60 minutes, then keeping at 180 ℃ for 20 minutes, then keeping at 200-240 ℃ for 60 minutes, and finally keeping at 370-390 ℃ for 10 minutes, thus obtaining the multifunctional polyimide composite film with the layered structure.
  5. 5. The method for preparing a multifunctional polyimide composite film having a layered structure according to claim 4, wherein the dianhydride monomer is selected from one or more of pyromellitic dianhydride, hydrogenated pyromellitic dianhydride, biphenyl tetracarboxylic dianhydride, diphenyl ether tetracarboxylic dianhydride, benzophenone tetracarboxylic dianhydride, 4' - (acetylene-1, 2-diyl) diphthalic anhydride, hexafluorodianhydride, and a compound having two anhydride functional groups.
  6. 6. The method for producing a multifunctional polyimide composite film having a layered structure according to claim 4, wherein the diamine monomer is one or more selected from the group consisting of 4,4' -diaminodiphenyl ether, p-phenylenediamine, 4' -diaminodiphenyl methane, m-phenylenediamine, 2-bis (trifluoromethyl) benzidine, 4-aminophenyl disulfide, 4' -dithio-diphenylamine and compounds having two or more amino functional groups.
  7. 7. The method for producing a multifunctional polyimide composite film having a layered structure according to claim 4, wherein the organic solvent is one or more selected from the group consisting of N, N-dimethylformamide, N-dimethylacetamide, methylpyrrolidone, and dimethylsulfoxide.
  8. 8. The method for producing a multifunctional polyimide composite film having a layered structure according to claim 4, wherein the equipment used for the defoaming treatment in S2 is a vacuum oven, a centrifugal defoaming machine, a self-made defoaming equipment or a vacuum defoaming machine.
  9. 9. The method for producing a multifunctional polyimide composite film having a layered structure according to claim 4, wherein the tool used for coating in S3 is a flat coater, a blade coater, or a bar coater.
  10. 10. The method of claim 4, wherein the flat plate in S3 is a glass plate, a marble plate, a ceramic tile plate, a stainless steel plate, a mica plate, or an aluminum silicate ceramic fiber plate.

Description

Multifunctional polyimide composite film with layered structure and preparation method thereof Technical Field The invention relates to the technical field of electronic packaging materials, in particular to a multifunctional polyimide composite film with a layered structure and a preparation method thereof. Background The polymer film material has wider application in the industries of biological medicine, packaging and printing, electronic packaging, new energy, separation and filtration and the like, and along with the application of the composite technology in the polymer film, the electronic packaging material, electromagnetic compatibility, thermal management material and the like have higher and higher requirements on the functions of the polymer film. Polyimide (PI) is a polymer with imide ring (-CO-N-CO-) on its main chain, and is one of the organic high molecular materials with optimal comprehensive properties. The polyimide has high temperature resistance of more than 400 ℃ and long-term use temperature range of-200-300 ℃, has the characteristics of radiation resistance, flame retardance and no toxicity, and has the advantages of good electrical insulation performance, mechanical performance, chemical stability, ageing resistance, low dielectric loss, excellent mechanical performance, dimensional stability, chemical stability, biocompatibility and the like. Polyimide films are very suitable for applications in flexible substrates, electromagnetic shielding, microelectronics, and other fields as one of the application forms. Under the high power density packaging background, the temperature of a hot spot of a chip rises, and the problem of electromagnetic interference is outstanding, but polyimide has very low heat conduction coefficient and very high electrical insulation property, and the requirements of quick heat dissipation and electromagnetic compatibility cannot be met. In general, high heat conduction and electric conduction fillers, such as carbon materials and metal materials, are introduced into polyimide, so that the heat conduction and electromagnetic shielding properties of the polyimide are synchronously improved. For example, a light flexible amino-functionalized multi-walled carbon nanotube-graphene nanoplatelet/poly (p-phenylbenzodioxazole)/poly (ether ketone) composite film prepared by a vacuum-assisted layer-by-layer filtration method is of a sandwich structure, has a thickness of 0.05mm, and shows excellent electromagnetic shielding performance and in-plane thermal conductivity (Small 2025, 21, 2503573). However, the preparation method of vacuum assisted filtration is time-consuming and labor-consuming, the layer thickness of the composite membrane is not well controlled, and industrial continuous production cannot be realized. Metal materials are more expensive than carbon materials, but metal materials have a high density and a large amount of filled polymer reduces the flexibility of the film. Therefore, metal nanoparticles, such as aluminum, are commonly sputtered on the surface of polyimide films in commerce to improve the electromagnetic shielding performance of polyimide composite films, but the coating cannot realize the heat conducting performance, and the sputtered metal layer is positioned on the surface of the film, so that the film is not acid corrosion resistant and has the risks of abrasion and falling off. Researchers often coat metal materials on the surfaces of polymer fibers to achieve electromagnetic shielding performance, for example, after polydopamine coarsening, chloroplatinic acid palladium-free activation, chemical nickel plating and octadecanethiol corrosion resistance treatment, novel light flexible metallized polyimide non-woven fabrics are prepared, excellent joule heating and electromagnetic shielding performance (CHEMICAL ENGINEERING Journal, 2024,480,148000) are achieved, the film has a porous structure, the coating of metal on the surfaces of the fibers keeps the mechanical performance of the composite film, but the preparation procedure is complex, and the existence of pores cannot conduct heat effectively. Furthermore, along with the expansion of application scenes to extreme and cold conditions such as deep sea, deep space and the like, the multifunctionality of polyimide is imperative, and a simple and convenient preparation and production mode capable of realizing the metal material in polyimide to meet the multifunctional requirements is needed. Disclosure of Invention In view of the problems in the prior art, it is an object of the present invention to provide a multifunctional polyimide composite film having a layered structure in which alloy powder is distributed in a certain layer thickness range near one surface of the polyimide composite film to form a layered structure. The composite film with the layered structure has the performances of photo-thermal conversion, electromagnetic shielding and in-plane heat conduction, and meets t