WO2022001952A1 - Electrically and thermally conductive adhesive film and preparation method and application thereof - Google Patents

Electrically and thermally conductive adhesive film and preparation method and application thereof Download PDF

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Publication number
WO2022001952A1
WO2022001952A1 PCT/CN2021/102744 CN2021102744W WO2022001952A1 WO 2022001952 A1 WO2022001952 A1 WO 2022001952A1 CN 2021102744 W CN2021102744 W CN 2021102744W WO 2022001952 A1 WO2022001952 A1 WO 2022001952A1
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Prior art keywords
adhesive
mesh
metal
film
silver
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PCT/CN2021/102744
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French (fr)
Chinese (zh)
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黄贵文
肖红梅
刘玉
渠成兵
李娜
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中国科学院理化技术研究所
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Publication of WO2022001952A1 publication Critical patent/WO2022001952A1/en

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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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form
    • B32B3/26—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer
    • B32B3/266—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer characterised by an apertured layer, the apertures going through the whole thickness of the layer, e.g. expanded metal, perforated layer, slit layer regular cells B32B3/12
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/18—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by features of a layer of foamed material
    • 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
    • C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
    • C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
    • C09J123/04—Homopolymers or copolymers of ethene
    • C09J123/08—Copolymers of ethene
    • 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
    • C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
    • C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
    • C09J123/04—Homopolymers or copolymers of ethene
    • C09J123/08—Copolymers of ethene
    • C09J123/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
    • C09J123/0853—Vinylacetate
    • 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
    • C09J167/00—Adhesives based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Adhesives based on derivatives of such polymers
    • C09J167/06—Unsaturated polyesters having carbon-to-carbon unsaturation
    • 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
    • C09J177/00—Adhesives based on polyamides obtained by reactions forming a carboxylic amide link in the main chain; Adhesives based on derivatives of such polymers
    • 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
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C08K2003/0806—Silver
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C08K2003/0862—Nickel
    • 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
    • C09J2400/00—Presence of inorganic and organic materials
    • C09J2400/10—Presence of inorganic materials
    • C09J2400/16—Metal

Definitions

  • the invention belongs to the technical field of material functionalized bonding, and in particular relates to a conductive and thermally conductive adhesive film and a preparation method and application thereof.
  • Adhesive bonding is an important technical means for connecting two material components in engineering applications.
  • the bonding of some components not only requires the bonding layer to provide mechanical connection, but also needs to have some special functions.
  • the connection between some electronic devices requires the adhesive layer to provide good electrical conductivity
  • the connection between some components that need to be dissipated in work and the heat sink requires the adhesive layer to have good thermal conductivity.
  • This requires functionalized adhesives, which not only have mechanical bonding properties, but also have functions such as electrical conductivity and thermal conductivity.
  • microscopic conductive and thermally conductive fillers are generally added to the adhesive matrix and make it reach a certain penetration threshold, thereby obtaining a functionalized adhesive.
  • Adhesive film is an adhesive that is prefabricated into a uniform film state and is solid or gel state at operating temperature. There is no need to apply glue in use, and the glue film can be directly pressed and cured at the interface between the objects to be adhered. Adhesive films conveniently provide a uniform, quantitative bond for a bond interface with good consistency. And the film can be cut at will, and can adapt to the bonding of different shapes of bonding surfaces. Therefore, adhesives in the form of film have outstanding advantages in practical engineering applications.
  • the preparation of the adhesive film is generally obtained by heating a thermosetting or thermoplastic adhesive to a temperature above the softening temperature and uniformly coating it on the release layer.
  • a thermosetting or thermoplastic adhesive For functionalized adhesive films such as electrical conductivity and thermal conductivity, it is generally obtained by fully mixing the microscopically conductive and thermally conductive fillers with the adhesive matrix and then coating.
  • the coated composite adhesive film is prone to filler agglomeration and uneven distribution. Causes instability of film performance.
  • the present invention provides a conductive and thermally conductive adhesive film
  • the conductive and thermally conductive adhesive film includes an adhesive matrix and a metal network
  • the metal network is embedded in the adhesive matrix
  • the length, width and height of the metal network are the same as those of the conductive and thermally conductive adhesive film
  • the length, width and height are the same.
  • the metal network is selected from at least one of metal foam and metal mesh, eg, the metal network is a metal foam film or a metal mesh.
  • the adhesive matrix fills (all) the pores of the metal foam film.
  • the adhesive matrix fills (all) meshes of the metal mesh and is in contact with (all) the metal mesh wires.
  • the foamed metal film is selected from at least one of the foamed nickel foam, foamed copper, foamed silver, foamed iron, foamed aluminum, foamed titanium, foamed iron-nickel, and at least one of the above-mentioned foamed metal films plated with silver or gold on the surface.
  • the foamed metal film is nickel foam, copper foam, silver foam, silver-plated nickel foam, and/or silver-plated copper foam.
  • the thickness of the foamed metal film is 0.02-2 mm, for example, the thickness is 0.05-0.15 mm, exemplarily 0.1 mm, 0.15 mm, 0.2 mm.
  • the porosity of the foamed metal film is 50-98%, such as 60-90%, exemplarily 60%, 70%, 80%, 90%, 95%.
  • the metal mesh is selected from at least one of nickel mesh, copper mesh, silver mesh, iron mesh, aluminum mesh, titanium mesh, iron-nickel mesh, and silver-plated or gold-plated surface metal meshes,
  • the metal mesh is a nickel mesh, a copper mesh, a silver mesh, a silver-coated copper mesh, and/or a silver-coated nickel mesh.
  • the thickness of the metal mesh is 0.02-2 mm, eg, 0.05-0.15 mm, exemplarily 0.1 mm, 0.15 mm, 0.2 mm.
  • the mesh number of the metal mesh is 40-800 mesh, such as 50-600 mesh, and exemplarily 100 mesh, 200 mesh, and 300 mesh.
  • the metal mesh may be selected from at least one of a metal wire woven mesh, a stretched mesh, a punched mesh, an etched mesh, and the like.
  • the conductive and thermally conductive adhesive film may contain the same or different metal networks superimposed together. For example, two layers of nickel mesh or one layer of nickel mesh and one layer of copper mesh are superimposed. Further, the thickness of the superimposed metal mesh is the same as the thickness of the conductive and thermally conductive adhesive film.
  • the adhesive matrix includes a thermoset adhesive and/or thermoplastic adhesive, and optionally, with or without electrically and/or thermally conductive fillers.
  • the present invention utilizes the continuous metal network structure to reduce the weight content of the conductive and/or thermally conductive fillers, thereby obtaining high bonding strength.
  • the thermosetting adhesive is selected from the group consisting of epoxy resins, phenolic resins, cyanate ester resins, unsaturated polyester resins, bismaleimide resins, thermosetting polyimide resins and polybenzoxanes At least one of oxazine resins; for example, epoxy resins and/or unsaturated polyester resins.
  • the thermoplastic adhesive is selected from polyethylene hot melt adhesive, polypropylene hot melt adhesive, ethylene and its copolymer hot melt adhesive, polyester hot melt adhesive, polyamide hot melt adhesive, polyurethane hot melt adhesive At least one of styrene-like hot melt adhesives, styrene and its block copolymer-based hot melt adhesives, and amorphous alpha-olefin copolymers (APAO); for example, polyamide (PA) hot melt adhesives and/or ethylene- Vinyl acetate copolymer (EVA) hot melt adhesive.
  • PA polyamide
  • EVA ethylene- Vinyl acetate copolymer
  • the electrically and/or thermally conductive filler is selected from the group consisting of flake metal powder, spherical metal powder, dendritic metal powder, gold nanowires, silver nanowires, copper nanowires, graphite, fibrous carbon powder , scaly carbon powder, graphene, carbon nanotubes, diamond, aluminum oxide, magnesium oxide, zinc oxide, beryllium oxide, nickel oxide, calcium oxide, silicon dioxide (crystalline form), aluminum nitride, boron nitride and carbide one or more of silicon.
  • the electrically and/or thermally conductive fillers are present in an amount of 0-90% by weight of the adhesive matrix, such as 10-80%, again such as 20-50%, exemplarily 0, 10%, 20% , 30%, 40%, 50%.
  • the thickness of the conductive and thermally conductive adhesive film is substantially the same as the thickness of the continuous metal network, such as 0.02-2mm, such as 0.05-0.15mm, exemplarily 0.1mm, 0.15mm, 0.2mm mm.
  • the volume resistivity of the electrically and thermally conductive adhesive film is less than 5.0 ⁇ 10 -4 ⁇ cm, preferably (1.1-2.5) ⁇ 10 -4 ⁇ cm, and exemplarily 1.2 ⁇ 10 -4 ⁇ ⁇ cm, 1.5 ⁇ 10 -4 ⁇ cm, 1.6 ⁇ 10 -4 ⁇ cm, 1.8 ⁇ 10 -4 ⁇ cm.
  • the thermal conductivity of the electrically and thermally conductive adhesive film is greater than 6W/(m ⁇ K), preferably 8-20W/(m ⁇ K), exemplarily 8W/(m ⁇ K), 9W /(m ⁇ K), 10W/(m ⁇ K), 10.5W/(m ⁇ K).
  • the conductive and thermally conductive adhesive film includes an epoxy resin adhesive matrix and a silver-plated nickel foam embedded therein, wherein the length, width and height of the silver-plated nickel foam are the same as the overall length, width and height of the adhesive film. respectively the same.
  • the conductive and thermally conductive adhesive film includes a polyamide adhesive matrix and a silver-coated copper mesh embedded therein, wherein the length, width and height of the silver-coated copper mesh are respectively the same as the overall length, width and height of the adhesive film. same.
  • the conductive and thermally conductive adhesive film includes an unsaturated polyester resin adhesive containing silver powder and foamed copper embedded therein, wherein the length, width and height of the foamed copper are the same as the overall length, width and height of the adhesive film. respectively the same.
  • the conductive and thermally conductive adhesive film includes an ethylene-vinyl acetate copolymer adhesive containing silicon carbide and a silver-plated nickel mesh embedded therein, wherein the length, width and height of the silver-plated nickel mesh are integral with the adhesive film The length, width and height are the same.
  • the present invention also provides a method for preparing the above-mentioned electrically conductive and thermally conductive adhesive film, comprising the steps of: (a) pressing the metal network into the softened adhesive base film, or (b) coating and infiltrating the softened adhesive base into the into the metal network, or (c) filling the softened adhesive matrix into the metal network under auxiliary pressure to obtain the electrically and thermally conductive adhesive film.
  • the adhesive matrix is compounded with the metal network, and the conductive and thermally conductive adhesive film is obtained after cooling.
  • the electrically and/or thermally conductive filler may or may not be included in the adhesive matrix.
  • option (a) includes prefabricating the adhesive matrix into an adhesive matrix film.
  • the thickness of the adhesive base film is the same as the thickness of the metal network.
  • the press-in described in (a) may utilize a flat press or a roll calender, or the like, to press the metal network into the adhesive base film.
  • the pressing may be hot pressing or calendering.
  • the temperature of the hot pressing is 80-150°C, such as 90-130°C, exemplarily 100°C, 110°C, and 120°C.
  • the pressure of the hot pressing is 3-10 MPa, for example, 4-8 MPa, exemplarily 5 MPa, 6 MPa, and 7 MPa.
  • the holding time of the hot pressing is 0.5-2 minutes, for example, 1 minute.
  • the temperature of the calendering is 80-150°C, such as 90-130°C, exemplarily 100°C, 110°C, and 120°C.
  • the gap between the calendering rolls in the calendering process is 0.1-0.3 mm, for example, 0.15-0.25 mm, and exemplarily 0.2 mm.
  • the speed of the calendering is 0.2-1 m/min, such as 0.4-0.8 m/min, exemplarily 0.5 m/min.
  • the softened adhesive base film and the metal network are stacked, and the metal network is pressed into the softened adhesive base film by hot pressing or calendering.
  • the softened adhesive matrix can be directly coated and penetrated into the metal network by means of a glue film machine or the like in the scheme (b).
  • the coating method is a known coating method in the art, such as roll coating.
  • the coating gap is 0.05-0.3 mm, such as 0.15-0.25 mm, and exemplarily 0.15 mm.
  • the coating temperature is 80-150°C, for example, 90-130°C, exemplarily 90°C, 100°C, 110°C, and 120°C.
  • the coating speed is 0.5-2 m/min, such as 0.7-1.5 m/min, exemplarily 1 m/min.
  • the auxiliary pressure in scheme (c) can be achieved by auxiliary means such as vacuum.
  • auxiliary means such as vacuum.
  • a molten adhesive matrix infiltrates the metal network under vacuum.
  • the conductive and/or thermally conductive fillers can be dispersed in the fluid-dynamic adhesive to obtain an adhesive matrix.
  • the present invention also provides the conductive and thermally conductive adhesive film prepared by the above method.
  • the present invention also provides the application of the electrically conductive and thermally conductive adhesive film in bonding electronic devices and/or electronic components, so as to realize the electrical and/or thermal conductivity function between the adherends on both sides of the adhesive film.
  • the conductive and thermally conductive adhesive film is directly contacted with the objects to be bonded on both sides.
  • the present invention provides a conductive and thermally conductive adhesive film with a novel structure.
  • the film uses a continuous metal network to replace the traditional microscopic conductive and thermally conductive fillers.
  • the film forming process can be simplified, and higher electrical and thermal conductivity can be obtained;
  • the weight content of fillers can be reduced to a certain extent, so as to obtain higher bonding strength.
  • the continuous metal network can ensure the consistency of the film structure, and obtain a functionalized film with good performance consistency.
  • the film has high electrical conductivity, thermal conductivity and adhesive properties. details as follows:
  • the continuous metal network structure is filled with the directions of length, width and height of the adhesive film, and it is in direct contact with the adherends on both sides during use, which can reduce the interface resistance and thermal resistance;
  • Example 1 is a schematic cross-sectional view of an adhesive film prepared by utilizing a foam metal film in Example 1;
  • FIG. 2 is a schematic cross-sectional view of an adhesive film prepared by using a metal mesh in Example 2.
  • FIG. 2 is a schematic cross-sectional view of an adhesive film prepared by using a metal mesh in Example 2.
  • the volume resistivity of the adhesive film was tested according to ISO16525, the thermal conductivity was tested according to ASTM E1461, and the shear strength was tested according to ISO-4587:2003.
  • the epoxy resin adhesive was heated to above the softening temperature and coated on the release paper with a film coating machine to prepare an epoxy resin adhesive film with a thickness of 0.1 mm, and the coating temperature was 110°C. After the film was cooled, it was cut into a film with a size of 20 cm ⁇ 30 cm.
  • the silver-plated nickel foam with a thickness of 0.1 mm and a porosity of 90% was similarly cut into a film of 20 cm ⁇ 30 cm.
  • the silver plating amount of the silver-plated nickel foam is 10% by weight of the nickel.
  • the silver-plated nickel foam and the epoxy resin film are bonded together, and placed between two release papers, and placed between the upper and lower flat plates of the flat plate press for hot pressing.
  • the hot pressing temperature was 100° C.
  • the pressure was 5 MPa
  • the pressure holding time was 1 minute.
  • the epoxy resin above the softening temperature penetrates into the pores of the silver-plated nickel foam. Because the foam metal has a certain compressive performance, the excess resin overflows from the side, and finally forms the thickness of the silver-plated foam.
  • the cross-sectional structure of the composite film with the same nickel is shown in Figure 1.
  • the performance test of the obtained adhesive film shows that the volume resistivity of the adhesive film is 1.8 ⁇ 10 -4 ⁇ cm, the thermal conductivity is 8W/(m ⁇ K), and the Al-Al lap shear strength is 23MPa.
  • a roll calender was used for film forming.
  • the polyamide (PA) adhesive is heated to above the softening temperature, and is coated on the release paper by a film coating machine and wound to make an adhesive base film with a thickness of 0.15mm and a width of 30cm.
  • the coating temperature is 140°C.
  • the silver-plated copper mesh with a thickness of 0.2mm, a mesh number of 300 meshes, and a width of 30cm is compounded with the adhesive base film, and then placed between the upper and lower layers of release paper, the thickness of which is 0.1mm, and is placed between the two layers of release paper.
  • the roll device is fed into a twin-roll calender for continuous hot calendering.
  • the calendering roll gap was controlled to be 0.4 mm
  • the calendering roll temperature was 130° C.
  • the calendering speed was 0.5 m/min.
  • the film is cooled and rolled to obtain a composite film with a thickness of 0.2 mm which is continuously produced, and its cross-sectional structure is shown in Figure 2.
  • the performance test of the obtained adhesive film shows that the volume resistivity of the adhesive film is 1.5 ⁇ 10 -4 ⁇ cm, the thermal conductivity is 10W/(m ⁇ K), and the Al-Al lap shear strength is 6MPa.
  • a copper foam with a thickness of 0.15 mm and a porosity of 85% was placed on a layer of release paper.
  • the unsaturated polyester resin adhesive is heated to 90° C. and fully stirred, and flake silver powder is added and dispersed uniformly to obtain an adhesive matrix, wherein the weight of flake silver powder is 30% of the total weight of the adhesive matrix.
  • the adhesive matrix was directly coated on the copper foam by a glue film machine, and the coating was applied by roll coating.
  • the coating gap was controlled to be 0.15 mm, the coating temperature was 90 °C, and the coating speed was 1 m/min. After coating, the adhesive film is cooled to obtain a formed composite adhesive film.
  • the performance test of the obtained adhesive film shows that the volume resistivity of the adhesive film is 1.2 ⁇ 10 -4 ⁇ cm, the thermal conductivity is 10.5W/(m ⁇ K), and the gold-gold lap shear strength is 24MPa.
  • a vacuum-assisted resin transfer molding method is used to form the adhesive film.
  • a silver-plated nickel mesh with a thickness of 0.15 mm and a mesh number of 200 was cut into a film of 30 cm ⁇ 40 cm.
  • the two nickel mesh films are overlapped and placed between the upper and lower release papers, and the thickness of the release papers is 0.1 mm.
  • the distance between the upper and lower flat plates of the cavity is 0.5 mm.
  • the ethylene-vinyl acetate copolymer (EVA) hot-melt adhesive is heated to 120 ° C to make it flowable, and silicon carbide powder is added and dispersed uniformly to obtain an adhesive matrix, wherein the weight of silicon carbide is the total adhesive matrix. 30% of the weight.
  • the molten adhesive matrix is connected to the mold cavity by piping.
  • the mold cavity is evacuated through the vacuum port of the mold cavity, and the adhesive matrix enters the mold cavity under the action of vacuum and infiltrates the silver-plated nickel mesh. After fully infiltrating the silver-plated nickel mesh, the mold is cooled to obtain a composite film.
  • the performance test of the obtained adhesive film shows that the volume resistivity of the adhesive film is 1.6 ⁇ 10 -4 ⁇ cm, the thermal conductivity is 9W/(m ⁇ K), and the Al-Al lap shear strength is 4.5MPa.
  • the epoxy resin adhesive is heated to 90° C. and fully stirred, and flake silver powder is added and dispersed uniformly to obtain an adhesive matrix, wherein the weight of the flake silver powder is 50% of the total weight of the adhesive matrix.
  • the adhesive matrix was directly coated on the release paper by a film machine, and the coating was carried out by roll coating.
  • the coating gap was controlled to be 0.1 mm, the coating temperature was 80 °C, and the coating speed was 1 m/min. After coating, the film is cooled to obtain a formed film.
  • the performance test of the obtained adhesive film shows that the volume resistivity of the adhesive film is 2.5 ⁇ 10 -4 ⁇ cm, the thermal conductivity is 5.5 W/(m ⁇ K), and the Al-Al lap shear strength is 12 MPa.

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Abstract

An electrically and thermally conductive adhesive film and a preparation method and an application thereof. The adhesive film comprises an adhesive matrix and a metal mesh; the metal mesh is embedded into the adhesive matrix, and the length, width, and height of the metal mesh are same as the length, width, and height of the whole adhesive film. The adhesive film is used for bonding materials to be bonded at two sides, and achieves the functions such as electrical conduction and thermal conduction. The continuous metal mesh is used, the adhesive film can obtain higher electrical conductivity, thermal conductivity, and bonding strength, reduce the volume and content of a filler, and can ensure structural consistence of the adhesive film.

Description

一种导电导热胶膜及其制备方法和应用A kind of conductive and thermally conductive adhesive film and its preparation method and application
本申请要求申请人于2020年6月28日向中国国家知识产权局提交的专利申请号为202010599636.8，发明名称为“一种导电导热胶膜及其制备方法和应用”的在先申请的优先权。所述在先申请的全文通过引用的方式结合于本申请中。This application requires the priority of the prior application with the patent application number of 202010599636.8 and the invention titled "An Electrically Conductive and Thermally Conductive Adhesive Film and its Preparation Method and Application" submitted by the applicant to the State Intellectual Property Office of China on June 28, 2020. The entire contents of said prior applications are incorporated herein by reference.
技术领域technical field
本发明属于材料功能化粘接技术领域，具体涉及一种导电导热胶膜及其制备方法和应用。The invention belongs to the technical field of material functionalized bonding, and in particular relates to a conductive and thermally conductive adhesive film and a preparation method and application thereof.
背景技术Background technique
胶粘剂粘接是工程应用中连接两个材料部件的一种重要技术手段。在实际应用中，一些部件的粘接不仅需要粘接层提供力学连接，还需要兼具一些特殊功能。如一些电子器件间的连接需要粘接层提供良好的导电性能，一些工作中需要散热的部件和散热片之间的连接则需要粘接层具有较好的导热性能。这就需要功能化的胶粘剂，在具有力学粘接性能的同时，拥有导电、导热等功能。为实现这一目标，一般是在胶粘剂基体中加入微观导电、导热填料，并使其达到一定的渗透阈值，从而得到功能化的胶粘剂。Adhesive bonding is an important technical means for connecting two material components in engineering applications. In practical applications, the bonding of some components not only requires the bonding layer to provide mechanical connection, but also needs to have some special functions. For example, the connection between some electronic devices requires the adhesive layer to provide good electrical conductivity, and the connection between some components that need to be dissipated in work and the heat sink requires the adhesive layer to have good thermal conductivity. This requires functionalized adhesives, which not only have mechanical bonding properties, but also have functions such as electrical conductivity and thermal conductivity. In order to achieve this goal, microscopic conductive and thermally conductive fillers are generally added to the adhesive matrix and make it reach a certain penetration threshold, thereby obtaining a functionalized adhesive.
在应用过程中，传统的胶粘剂需要在被粘接物表面进行涂胶，然后将被粘接物压合进行粘接。但施胶的过程可能会由于操作的差异造成胶层不均匀或不定量，导致在批量的部件粘接中出现粘接性能的不稳定。基于此问题，发展出了胶膜形式的胶粘剂。胶膜是预制成均匀薄膜状态的，在操作温度下呈固态或凝胶态的一种胶粘剂。在使用中无需涂胶，直接将胶膜置于被粘接物间的界面压合固化即可。胶膜可以方便地提供均匀、定量的粘接层，以获得具有良好一 致性的粘接界面。并且胶膜可以随意裁剪，可适应不同形状粘接面的粘接。因此，胶膜形式的胶粘剂在实际工程应用中具有突出的优势。In the application process, the traditional adhesive needs to be glued on the surface of the adherend, and then the adherend is pressed for bonding. However, the process of gluing may cause uneven or inhomogeneous glue layer due to differences in operation, resulting in unstable bonding performance in the bonding of batches of parts. Based on this problem, adhesives in the form of films have been developed. Adhesive film is an adhesive that is prefabricated into a uniform film state and is solid or gel state at operating temperature. There is no need to apply glue in use, and the glue film can be directly pressed and cured at the interface between the objects to be adhered. Adhesive films conveniently provide a uniform, quantitative bond for a bond interface with good consistency. And the film can be cut at will, and can adapt to the bonding of different shapes of bonding surfaces. Therefore, adhesives in the form of film have outstanding advantages in practical engineering applications.
胶膜的制备一般是将热固性或热塑性的胶粘剂加热至软化温度以上在离型层上均匀涂布而得到。对于导电、导热等功能化的胶膜，一般是将微观导电导热填料与胶粘剂基体充分混合后再进行涂布得到。但是由于胶膜的胶粘剂基体一般粘度较大，将微观填料与胶粘剂基体在软化温度以上混合时工艺难度较大，并且涂布得到的复合胶膜容易出现填料团聚、分布不均匀等问题，从而会造成胶膜性能的不稳定。The preparation of the adhesive film is generally obtained by heating a thermosetting or thermoplastic adhesive to a temperature above the softening temperature and uniformly coating it on the release layer. For functionalized adhesive films such as electrical conductivity and thermal conductivity, it is generally obtained by fully mixing the microscopically conductive and thermally conductive fillers with the adhesive matrix and then coating. However, due to the generally high viscosity of the adhesive matrix of the adhesive film, it is difficult to mix the microscopic filler and the adhesive matrix above the softening temperature, and the coated composite adhesive film is prone to filler agglomeration and uneven distribution. Causes instability of film performance.
发明内容SUMMARY OF THE INVENTION
本发明提供一种导电导热胶膜，所述导电导热胶膜包括胶粘剂基体和金属网络，所述金属网络嵌入在胶粘剂基体中，且金属网络的长、宽、高与所述导电导热胶膜的长、宽、高分别相同。The present invention provides a conductive and thermally conductive adhesive film, the conductive and thermally conductive adhesive film includes an adhesive matrix and a metal network, the metal network is embedded in the adhesive matrix, and the length, width and height of the metal network are the same as those of the conductive and thermally conductive adhesive film The length, width and height are the same.
根据本发明的实施方案，所述金属网络选自泡沫金属和金属网中的至少一种，例如所述金属网络为泡沫金属膜或金属网。According to an embodiment of the present invention, the metal network is selected from at least one of metal foam and metal mesh, eg, the metal network is a metal foam film or a metal mesh.
根据本发明的实施方案，所述金属网络为泡沫金属膜时，所述胶粘剂基体充满所述泡沫金属膜的(所有)孔隙。According to an embodiment of the invention, when the metal network is a metal foam film, the adhesive matrix fills (all) the pores of the metal foam film.
根据本发明的实施方案，所述金属网络为金属网时，所述胶粘剂基体充满所述金属网的(所有)网孔，并与(所有)金属网丝接触。According to an embodiment of the present invention, when the metal network is a metal mesh, the adhesive matrix fills (all) meshes of the metal mesh and is in contact with (all) the metal mesh wires.
根据本发明的实施方案，所述泡沫金属膜选自泡沫镍、泡沫铜、泡沫银、泡沫铁、泡沫铝、泡沫钛、泡沫铁镍以及表面镀银或镀金的上述泡沫金属膜中的至少一种，例如所述泡沫金属膜为泡沫镍、泡沫铜、泡沫银、镀银泡沫镍、和/或镀银泡沫铜。According to an embodiment of the present invention, the foamed metal film is selected from at least one of the foamed nickel foam, foamed copper, foamed silver, foamed iron, foamed aluminum, foamed titanium, foamed iron-nickel, and at least one of the above-mentioned foamed metal films plated with silver or gold on the surface. For example, the foamed metal film is nickel foam, copper foam, silver foam, silver-plated nickel foam, and/or silver-plated copper foam.
根据本发明的实施方案，所述泡沫金属膜的厚度为0.02-2mm，例如厚度为0.05-0.15mm，示例性为0.1mm、0.15mm、0.2mm。According to an embodiment of the present invention, the thickness of the foamed metal film is 0.02-2 mm, for example, the thickness is 0.05-0.15 mm, exemplarily 0.1 mm, 0.15 mm, 0.2 mm.
根据本发明的实施方案，所述泡沫金属膜的孔隙率为50-98％，例如60-90％， 示例性为60％、70％、80％、90％、95％。According to an embodiment of the present invention, the porosity of the foamed metal film is 50-98%, such as 60-90%, exemplarily 60%, 70%, 80%, 90%, 95%.
根据本发明的实施方案，所述金属网选自镍网、铜网、银网、铁网、铝网、钛网、铁镍网以及表面镀银或镀金的上述金属网中的至少一种，例如所述金属网为镍网、铜网、银网、镀银铜网、和/或镀银镍网。According to an embodiment of the present invention, the metal mesh is selected from at least one of nickel mesh, copper mesh, silver mesh, iron mesh, aluminum mesh, titanium mesh, iron-nickel mesh, and silver-plated or gold-plated surface metal meshes, For example, the metal mesh is a nickel mesh, a copper mesh, a silver mesh, a silver-coated copper mesh, and/or a silver-coated nickel mesh.
根据本发明的实施方案，所述金属网的厚度为0.02-2mm，例如厚度为0.05-0.15mm，示例性为0.1mm、0.15mm、0.2mm。According to an embodiment of the present invention, the thickness of the metal mesh is 0.02-2 mm, eg, 0.05-0.15 mm, exemplarily 0.1 mm, 0.15 mm, 0.2 mm.
根据本发明的实施方案，所述金属网的网孔目数为40-800目，例如50-600目，示例性为100目、200目、300目。According to an embodiment of the present invention, the mesh number of the metal mesh is 40-800 mesh, such as 50-600 mesh, and exemplarily 100 mesh, 200 mesh, and 300 mesh.
根据本发明的实施方案，所述金属网可以选自金属丝编织网、拉伸网、冲孔网和蚀刻网等中的至少一种。According to an embodiment of the present invention, the metal mesh may be selected from at least one of a metal wire woven mesh, a stretched mesh, a punched mesh, an etched mesh, and the like.
根据本发明的实施方案，所述导电导热胶膜中可以含有叠加在一起的相同或不同的金属网络。例如两层镍网或一层镍网和一层铜网叠加，进一步地，叠加的金属网络的厚度与所述导电导热胶膜的厚度相同。According to an embodiment of the present invention, the conductive and thermally conductive adhesive film may contain the same or different metal networks superimposed together. For example, two layers of nickel mesh or one layer of nickel mesh and one layer of copper mesh are superimposed. Further, the thickness of the superimposed metal mesh is the same as the thickness of the conductive and thermally conductive adhesive film.
根据本发明的实施方案，所述胶粘剂基体包括热固性胶粘剂和/或热塑性胶粘剂，以及任选含有或不含有的导电和/或导热填料。本发明利用连续金属网络结构可以降低导电和/或导热填料的重量含量，从而获得高的粘接强度。According to an embodiment of the present invention, the adhesive matrix includes a thermoset adhesive and/or thermoplastic adhesive, and optionally, with or without electrically and/or thermally conductive fillers. The present invention utilizes the continuous metal network structure to reduce the weight content of the conductive and/or thermally conductive fillers, thereby obtaining high bonding strength.
根据本发明的实施方案，所述热固性胶粘剂选自环氧树脂、酚醛树脂、氰酸酯树脂、不饱和聚酯树脂、双马来酰亚胺树脂、热固性聚酰亚胺树脂和聚苯并恶嗪树脂中的至少一种；例如为环氧树脂和/或不饱和聚酯树脂。According to an embodiment of the present invention, the thermosetting adhesive is selected from the group consisting of epoxy resins, phenolic resins, cyanate ester resins, unsaturated polyester resins, bismaleimide resins, thermosetting polyimide resins and polybenzoxanes At least one of oxazine resins; for example, epoxy resins and/or unsaturated polyester resins.
根据本发明的实施方案，所述热塑性胶粘剂选自聚乙烯热熔胶、聚丙烯热熔胶、乙烯及其共聚物类热熔胶、聚酯类热熔胶、聚酰胺类热熔胶、聚氨酯类热熔胶、苯乙烯及其嵌段共聚物类热熔胶以及非晶态α-烯烃共聚物(APAO)中的至少一种；例如为聚酰胺(PA)热熔胶和/或乙烯-醋酸乙烯共聚物(EVA)热熔胶。According to an embodiment of the present invention, the thermoplastic adhesive is selected from polyethylene hot melt adhesive, polypropylene hot melt adhesive, ethylene and its copolymer hot melt adhesive, polyester hot melt adhesive, polyamide hot melt adhesive, polyurethane hot melt adhesive At least one of styrene-like hot melt adhesives, styrene and its block copolymer-based hot melt adhesives, and amorphous alpha-olefin copolymers (APAO); for example, polyamide (PA) hot melt adhesives and/or ethylene- Vinyl acetate copolymer (EVA) hot melt adhesive.
根据本发明的实施方案，所述导电和/或导热填料选自包括片状金属粉、球状金属粉、树枝状金属粉、金纳米线、银纳米线、铜纳米线、石墨、纤维状碳 粉、鳞片状碳粉、石墨烯、碳纳米管、金刚石、氧化铝、氧化镁、氧化锌、氧化铍、氧化镍、氧化钙、二氧化硅(结晶型)、氮化铝、氮化硼和碳化硅中的一种或多种。According to an embodiment of the present invention, the electrically and/or thermally conductive filler is selected from the group consisting of flake metal powder, spherical metal powder, dendritic metal powder, gold nanowires, silver nanowires, copper nanowires, graphite, fibrous carbon powder , scaly carbon powder, graphene, carbon nanotubes, diamond, aluminum oxide, magnesium oxide, zinc oxide, beryllium oxide, nickel oxide, calcium oxide, silicon dioxide (crystalline form), aluminum nitride, boron nitride and carbide one or more of silicon.
根据本发明的实施方案，所述导电和/或导热填料的重量占胶粘剂基体重量的0-90％，例如10-80％，又如20-50％，示例性为0、10％、20％、30％、40％、50％。According to an embodiment of the present invention, the electrically and/or thermally conductive fillers are present in an amount of 0-90% by weight of the adhesive matrix, such as 10-80%, again such as 20-50%, exemplarily 0, 10%, 20% , 30%, 40%, 50%.
根据本发明的实施方案，所述导电导热胶膜的厚度与所述连续金属网络的厚度基本相同，例如为0.02-2mm，例如厚度为0.05-0.15mm，示例性为0.1mm、0.15mm、0.2mm。According to an embodiment of the present invention, the thickness of the conductive and thermally conductive adhesive film is substantially the same as the thickness of the continuous metal network, such as 0.02-2mm, such as 0.05-0.15mm, exemplarily 0.1mm, 0.15mm, 0.2mm mm.
根据本发明的实施方案，所述导电导热胶膜的体积电阻率小于5.0×10 -4Ω·cm，优选(1.1-2.5)×10 -4Ω·cm，示例性为1.2×10 -4Ω·cm、1.5×10 -4Ω·cm、1.6×10 -4Ω·cm、1.8×10 -4Ω·cm。 According to an embodiment of the present invention, the volume resistivity of the electrically and thermally conductive adhesive film is less than 5.0×10 -4 Ω·cm, preferably (1.1-2.5)×10 -4 Ω·cm, and exemplarily 1.2×10 -4 Ω ·cm, 1.5×10 -4 Ω·cm, 1.6×10 -4 Ω·cm, 1.8×10 -4 Ω·cm.
根据本发明的实施方案，所述导电导热胶膜的热导率大于6W/(m·K)，优选为8-20W/(m·K)，示例性为8W/(m·K)、9W/(m·K)、10W/(m·K)、10.5W/(m·K)。According to an embodiment of the present invention, the thermal conductivity of the electrically and thermally conductive adhesive film is greater than 6W/(m·K), preferably 8-20W/(m·K), exemplarily 8W/(m·K), 9W /(m·K), 10W/(m·K), 10.5W/(m·K).
根据本发明示例性的方案，所述导电导热胶膜包括环氧树脂胶粘剂基体和嵌入其中的镀银泡沫镍，其中镀银泡沫镍的长、宽、高与胶膜整体的长、宽、高分别相同。According to an exemplary solution of the present invention, the conductive and thermally conductive adhesive film includes an epoxy resin adhesive matrix and a silver-plated nickel foam embedded therein, wherein the length, width and height of the silver-plated nickel foam are the same as the overall length, width and height of the adhesive film. respectively the same.
根据本发明示例性的方案，所述导电导热胶膜包括聚酰胺胶粘剂基体和嵌入其中的镀银铜网，其中镀银铜网的长、宽、高与胶膜整体的长、宽、高分别相同。According to an exemplary solution of the present invention, the conductive and thermally conductive adhesive film includes a polyamide adhesive matrix and a silver-coated copper mesh embedded therein, wherein the length, width and height of the silver-coated copper mesh are respectively the same as the overall length, width and height of the adhesive film. same.
根据本发明示例性的方案，所述导电导热胶膜包括含有银粉的不饱和聚酯树脂胶粘剂和嵌入其中的泡沫铜，其中泡沫铜的长、宽、高与胶膜整体的长、宽、高分别相同。According to an exemplary solution of the present invention, the conductive and thermally conductive adhesive film includes an unsaturated polyester resin adhesive containing silver powder and foamed copper embedded therein, wherein the length, width and height of the foamed copper are the same as the overall length, width and height of the adhesive film. respectively the same.
根据本发明示例性的方案，所述导电导热胶膜包括含有碳化硅的乙烯-醋酸乙烯共聚物胶粘剂和嵌入其中的镀银镍网，其中镀银镍网的长、宽、高与胶膜整体的长、宽、高分别相同。According to an exemplary solution of the present invention, the conductive and thermally conductive adhesive film includes an ethylene-vinyl acetate copolymer adhesive containing silicon carbide and a silver-plated nickel mesh embedded therein, wherein the length, width and height of the silver-plated nickel mesh are integral with the adhesive film The length, width and height are the same.
本发明还提供上述导电导热胶膜的制备方法，包括如下步骤：(a)将所述 金属网络压入软化的胶粘剂基体膜中，或者(b)将软化的胶粘剂基体涂覆并渗透至所述金属网络中，或者(c)在辅助压力下将软化的胶粘剂基体填充至所述金属网络中，得到所述导电导热胶膜。The present invention also provides a method for preparing the above-mentioned electrically conductive and thermally conductive adhesive film, comprising the steps of: (a) pressing the metal network into the softened adhesive base film, or (b) coating and infiltrating the softened adhesive base into the into the metal network, or (c) filling the softened adhesive matrix into the metal network under auxiliary pressure to obtain the electrically and thermally conductive adhesive film.
根据本发明的实施方案，上述方法中使胶粘剂基体与金属网络复合，冷却后得到所述导电导热胶膜。According to an embodiment of the present invention, in the above method, the adhesive matrix is compounded with the metal network, and the conductive and thermally conductive adhesive film is obtained after cooling.
所述胶粘剂基体中任选含有或不含有所述导电和/或导热填料。The electrically and/or thermally conductive filler may or may not be included in the adhesive matrix.
根据本发明的实施方案，方案(a)中包括将胶粘剂基体预制成胶粘剂基体膜。优选地，所述胶粘剂基体膜的厚度与所述金属网络的厚度相同。According to an embodiment of the invention, option (a) includes prefabricating the adhesive matrix into an adhesive matrix film. Preferably, the thickness of the adhesive base film is the same as the thickness of the metal network.
根据本发明的实施方案，方案(a)中所述压入可以利用平板压力机或辊式压延机等，将金属网络压入胶粘剂基体膜中。According to an embodiment of the present invention, the press-in described in (a) may utilize a flat press or a roll calender, or the like, to press the metal network into the adhesive base film.
根据本发明的实施方案，方案(a)中，所述压入可以为热压或压延。According to an embodiment of the present invention, in scheme (a), the pressing may be hot pressing or calendering.
根据本发明的实施方案，方案(a)中，所述热压的温度为80-150℃，例如90-130℃，示例性为100℃、110℃、120℃。其中，所述热压的压力为3-10MPa，例如4-8MPa，示例性为5MPa、6MPa、7MPa。其中，所述热压的保压时间为0.5-2分钟，例如1分钟。According to an embodiment of the present invention, in scheme (a), the temperature of the hot pressing is 80-150°C, such as 90-130°C, exemplarily 100°C, 110°C, and 120°C. Wherein, the pressure of the hot pressing is 3-10 MPa, for example, 4-8 MPa, exemplarily 5 MPa, 6 MPa, and 7 MPa. Wherein, the holding time of the hot pressing is 0.5-2 minutes, for example, 1 minute.
根据本发明的实施方案，方案(a)中，所述压延的温度为80-150℃，例如90-130℃，示例性为100℃、110℃、120℃。其中，所述压延过程中压延辊的间隙为0.1-0.3mm，例如0.15-0.25mm，示例性为0.2mm。其中，所述压延的速度为0.2-1m/min，例如0.4-0.8m/min，示例性为0.5m/min。According to an embodiment of the present invention, in scheme (a), the temperature of the calendering is 80-150°C, such as 90-130°C, exemplarily 100°C, 110°C, and 120°C. Wherein, the gap between the calendering rolls in the calendering process is 0.1-0.3 mm, for example, 0.15-0.25 mm, and exemplarily 0.2 mm. Wherein, the speed of the calendering is 0.2-1 m/min, such as 0.4-0.8 m/min, exemplarily 0.5 m/min.
根据本发明的实施方案，方案(a)中将软化的胶粘剂基体膜和金属网络叠放，通过热压或压延，使金属网络压入软化的胶粘剂基体膜中。According to an embodiment of the present invention, in option (a), the softened adhesive base film and the metal network are stacked, and the metal network is pressed into the softened adhesive base film by hot pressing or calendering.
根据本发明的实施方案，方案(b)中可以利用胶膜机等直接将软化的胶粘剂基体涂布并渗透至金属网络中。According to an embodiment of the present invention, the softened adhesive matrix can be directly coated and penetrated into the metal network by means of a glue film machine or the like in the scheme (b).
根据本发明的实施方案，方案(b)中，所述涂布的方式为本领域已知涂布方式，例如辊压涂布。其中，涂布间隙为0.05-0.3mm，例如0.15-0.25mm，示例性为0.15mm。其中，涂布的温度为80-150℃，例如90-130℃，示例性为90℃、 100℃、110℃、120℃。其中，涂布的速度为0.5-2m/min，例如0.7-1.5m/min，示例性为1m/min。According to an embodiment of the present invention, in scheme (b), the coating method is a known coating method in the art, such as roll coating. Wherein, the coating gap is 0.05-0.3 mm, such as 0.15-0.25 mm, and exemplarily 0.15 mm. Wherein, the coating temperature is 80-150°C, for example, 90-130°C, exemplarily 90°C, 100°C, 110°C, and 120°C. Wherein, the coating speed is 0.5-2 m/min, such as 0.7-1.5 m/min, exemplarily 1 m/min.
根据本发明的实施方案，方案(c)中所述辅助压力可以由真空等辅助手段来实现。例如，熔融的胶粘剂基体在真空作用下浸润所述金属网络。According to an embodiment of the present invention, the auxiliary pressure in scheme (c) can be achieved by auxiliary means such as vacuum. For example, a molten adhesive matrix infiltrates the metal network under vacuum.
根据本发明的实施方案，当所述胶粘剂基体中含有导电和/或导热填料时，可以将导电和/或导热填料分散于流动态的胶粘剂中，得到胶粘剂基体。According to an embodiment of the present invention, when the adhesive matrix contains conductive and/or thermally conductive fillers, the conductive and/or thermally conductive fillers can be dispersed in the fluid-dynamic adhesive to obtain an adhesive matrix.
本发明还提供由上述方法制备得到的导电导热胶膜。The present invention also provides the conductive and thermally conductive adhesive film prepared by the above method.
本发明还提供所述导电导热胶膜在粘结电子器件和/或电子元件中的应用，以实现胶膜两侧被粘接物间的导电和/或导热功能。优选地，粘结时，直接将导电导热胶膜与两侧被粘结物接触。The present invention also provides the application of the electrically conductive and thermally conductive adhesive film in bonding electronic devices and/or electronic components, so as to realize the electrical and/or thermal conductivity function between the adherends on both sides of the adhesive film. Preferably, when bonding, the conductive and thermally conductive adhesive film is directly contacted with the objects to be bonded on both sides.
本发明的有益效果：Beneficial effects of the present invention:
本发明提供了一种具有新型结构的导电导热胶膜。该胶膜利用连续的金属网络替代传统微观导电导热填料，一方面，可以简化胶膜成型工艺，并可获得更高的电导率和热导率；另一方面，使用连续的金属网络可以在一定程度上降低填料的重量含量，从而获得更高的粘接强度。并且，连续的金属网络可以保证胶膜结构的一致性，得到性能一致性好的功能化胶膜。同时使胶膜具有高的导电、导热及粘接性能。具体如下：The present invention provides a conductive and thermally conductive adhesive film with a novel structure. The film uses a continuous metal network to replace the traditional microscopic conductive and thermally conductive fillers. On the one hand, the film forming process can be simplified, and higher electrical and thermal conductivity can be obtained; The weight content of fillers can be reduced to a certain extent, so as to obtain higher bonding strength. In addition, the continuous metal network can ensure the consistency of the film structure, and obtain a functionalized film with good performance consistency. At the same time, the film has high electrical conductivity, thermal conductivity and adhesive properties. details as follows:
1)利用连续的金属网络结构可以获得高的电导率和热导率；1) High electrical and thermal conductivity can be obtained by using a continuous metal network structure;
2)连续的金属网络结构充满胶膜的、长、宽和高的方向，并且在使用过程中直接与两侧被粘接物接触，可以降低界面电阻和热阻；2) The continuous metal network structure is filled with the directions of length, width and height of the adhesive film, and it is in direct contact with the adherends on both sides during use, which can reduce the interface resistance and thermal resistance;
3)利用连续的金属网络结构可以降低填料的重量含量，从而获得高的粘接强度；3) The use of continuous metal network structure can reduce the weight content of fillers, thereby obtaining high bonding strength;
4)利用连续的金属网络结构可以保证胶膜性能的一致性。4) The use of a continuous metal network structure can ensure the consistency of film properties.
附图说明Description of drawings
图1是实施例1中利用泡沫金属薄膜制备的胶膜断面示意图；1 is a schematic cross-sectional view of an adhesive film prepared by utilizing a foam metal film in Example 1;
图2是实施例2中利用金属网制备的胶膜断面示意图。2 is a schematic cross-sectional view of an adhesive film prepared by using a metal mesh in Example 2. FIG.
具体实施方式detailed description
下文将结合具体实施例对本发明的技术方案做更进一步的详细说明。应当理解，下列实施例仅为示例性地说明和解释本发明，而不应被解释为对本发明保护范围的限制。凡基于本发明上述内容所实现的技术均涵盖在本发明旨在保护的范围内。The technical solutions of the present invention will be described in further detail below with reference to specific embodiments. It should be understood that the following examples are only for illustrating and explaining the present invention, and should not be construed as limiting the protection scope of the present invention. All technologies implemented based on the above content of the present invention are covered within the intended protection scope of the present invention.
除非另有说明，以下实施例中使用的原料和试剂均为市售商品，或者可以通过已知方法制备。Unless otherwise stated, the starting materials and reagents used in the following examples are commercially available or can be prepared by known methods.
实施例中胶膜的体积电阻率依据ISO16525测试，热导率依据ASTM E1461测试，剪切强度依据ISO-4587:2003测试。In the examples, the volume resistivity of the adhesive film was tested according to ISO16525, the thermal conductivity was tested according to ASTM E1461, and the shear strength was tested according to ISO-4587:2003.
实施例1Example 1
此实施例中使用平板压力机进行胶膜成型。In this example, a flatbed press was used for film forming.
将环氧树脂胶粘剂加热至软化温度以上并利用涂膜机将其涂布于离型纸上，制成厚度为0.1mm的环氧树脂胶膜，涂布温度为110℃。胶膜冷却后，将其剪裁成尺寸为20cm×30cm的薄膜。The epoxy resin adhesive was heated to above the softening temperature and coated on the release paper with a film coating machine to prepare an epoxy resin adhesive film with a thickness of 0.1 mm, and the coating temperature was 110°C. After the film was cooled, it was cut into a film with a size of 20 cm × 30 cm.
将厚度为0.1mm，孔隙率为90％的镀银泡沫镍同样裁剪为20cm×30cm的薄膜。镀银泡沫镍的镀银量为镍重量的10％。The silver-plated nickel foam with a thickness of 0.1 mm and a porosity of 90% was similarly cut into a film of 20 cm×30 cm. The silver plating amount of the silver-plated nickel foam is 10% by weight of the nickel.
将镀银泡沫镍与环氧树脂胶膜贴合在一起，并置于两张离型纸之间，放置于平板压力机的上下两平板之间，进行热压。热压温度为100℃，压力为5MPa，保压时间为1分钟。在压力作用下，在软化温度之上的环氧树脂渗透至镀银泡沫镍的孔隙之中，由于泡沫金属具有一定的抗压性能，多余的树脂从侧边溢出，最终形成厚度与镀银泡沫镍相同的复合胶膜，其断面结构如图1所示。The silver-plated nickel foam and the epoxy resin film are bonded together, and placed between two release papers, and placed between the upper and lower flat plates of the flat plate press for hot pressing. The hot pressing temperature was 100° C., the pressure was 5 MPa, and the pressure holding time was 1 minute. Under the action of pressure, the epoxy resin above the softening temperature penetrates into the pores of the silver-plated nickel foam. Because the foam metal has a certain compressive performance, the excess resin overflows from the side, and finally forms the thickness of the silver-plated foam. The cross-sectional structure of the composite film with the same nickel is shown in Figure 1.
对获得的胶膜进行性能测试，该胶膜的体积电阻率为1.8×10 -4Ω·cm，热导率为8W/(m·K)，铝-铝搭接剪切强度为23MPa。 The performance test of the obtained adhesive film shows that the volume resistivity of the adhesive film is 1.8×10 -4 Ω·cm, the thermal conductivity is 8W/(m·K), and the Al-Al lap shear strength is 23MPa.
实施例2Example 2
此实施例中使用辊式压延机进行胶膜成型。In this example, a roll calender was used for film forming.
将聚酰胺(PA)胶粘剂加热至软化温度以上并利用涂膜机将其涂布于离型纸上并收卷，制成厚度为0.15mm，幅宽为30cm的胶粘剂基体胶膜，涂布温度为140℃。The polyamide (PA) adhesive is heated to above the softening temperature, and is coated on the release paper by a film coating machine and wound to make an adhesive base film with a thickness of 0.15mm and a width of 30cm. The coating temperature is 140°C.
将厚度为0.2mm，目数为300目，幅宽为30cm的镀银铜网与胶粘剂基体胶膜复合后置于上下两层离型纸之间，离型纸厚度为0.1mm，并通过放卷装置送入双辊式压延机进行连续热压延。控制压延辊间隙为0.4mm，压延辊温度为130℃，压延速度为0.5m/min。压延后将胶膜冷却并收卷，得到厚度为0.2mm连续生产的复合胶膜，其断面结构如图2所示。The silver-plated copper mesh with a thickness of 0.2mm, a mesh number of 300 meshes, and a width of 30cm is compounded with the adhesive base film, and then placed between the upper and lower layers of release paper, the thickness of which is 0.1mm, and is placed between the two layers of release paper. The roll device is fed into a twin-roll calender for continuous hot calendering. The calendering roll gap was controlled to be 0.4 mm, the calendering roll temperature was 130° C., and the calendering speed was 0.5 m/min. After calendering, the film is cooled and rolled to obtain a composite film with a thickness of 0.2 mm which is continuously produced, and its cross-sectional structure is shown in Figure 2.
对获得的胶膜进行性能测试，该胶膜的体积电阻率为1.5×10 -4Ω·cm，热导率为10W/(m·K)，铝-铝搭接剪切强度为6MPa。 The performance test of the obtained adhesive film shows that the volume resistivity of the adhesive film is 1.5×10 -4 Ω·cm, the thermal conductivity is 10W/(m·K), and the Al-Al lap shear strength is 6MPa.
实施例3Example 3
此实施例中使用胶膜机进行胶膜成型。In this example, a glue film machine was used for film forming.
将厚度为0.15mm，孔隙率为85％的泡沫铜置于一层离型纸上。将不饱和聚酯树脂胶粘剂加热至90℃并充分搅拌，加入片状银粉并分散均匀，得到胶粘剂基体，其中片状银粉重量为胶粘剂基体总重量的30％。利用胶膜机将胶粘剂基体直接涂布于泡沫铜上，涂布采用辊压涂布的方式，控制涂布间隙为0.15mm，涂布温度为90℃，涂布速度为1m/min。涂布后待胶膜冷却得到成型的复合胶膜。A copper foam with a thickness of 0.15 mm and a porosity of 85% was placed on a layer of release paper. The unsaturated polyester resin adhesive is heated to 90° C. and fully stirred, and flake silver powder is added and dispersed uniformly to obtain an adhesive matrix, wherein the weight of flake silver powder is 30% of the total weight of the adhesive matrix. The adhesive matrix was directly coated on the copper foam by a glue film machine, and the coating was applied by roll coating. The coating gap was controlled to be 0.15 mm, the coating temperature was 90 °C, and the coating speed was 1 m/min. After coating, the adhesive film is cooled to obtain a formed composite adhesive film.
对获得的胶膜进行性能测试，该胶膜的体积电阻率为1.2×10 -4Ω·cm，热导率为10.5W/(m·K)，金-金搭接剪切强度为24MPa。 The performance test of the obtained adhesive film shows that the volume resistivity of the adhesive film is 1.2×10 -4 Ω·cm, the thermal conductivity is 10.5W/(m·K), and the gold-gold lap shear strength is 24MPa.
实施例4Example 4
此实施例中采用真空辅助树脂传递成型方式进行胶膜成型。In this embodiment, a vacuum-assisted resin transfer molding method is used to form the adhesive film.
将厚度为0.15mm，目数为200目的镀银镍网裁剪成30cm×40cm的薄膜。将两张镍网薄膜重叠并放置于上下两张离型纸之间，离型纸厚度为0.1mm。将叠放好的镍网与离型纸放入真空辅助成型的平板模腔中并将模具预热至120℃，模 腔上下平板的间距为0.5mm。A silver-plated nickel mesh with a thickness of 0.15 mm and a mesh number of 200 was cut into a film of 30 cm×40 cm. The two nickel mesh films are overlapped and placed between the upper and lower release papers, and the thickness of the release papers is 0.1 mm. Put the stacked nickel mesh and release paper into the flat cavity of vacuum-assisted forming, and preheat the mold to 120°C. The distance between the upper and lower flat plates of the cavity is 0.5 mm.
在另一容器中将乙烯-醋酸乙烯共聚物(EVA)热熔胶加热至120℃使其呈可流动态，加入碳化硅粉体并分散均匀，得到胶粘剂基体，其中碳化硅重量为胶粘剂基体总重量的30％。通过管道将熔融的胶粘剂基体与模腔连接。通过模腔的真空口对模腔抽真空，则胶粘剂基体在真空作用下进入模腔并浸润镀银镍网。在充分浸润镀银镍网后，将模具冷却降温即得到复合胶膜。In another container, the ethylene-vinyl acetate copolymer (EVA) hot-melt adhesive is heated to 120 ° C to make it flowable, and silicon carbide powder is added and dispersed uniformly to obtain an adhesive matrix, wherein the weight of silicon carbide is the total adhesive matrix. 30% of the weight. The molten adhesive matrix is connected to the mold cavity by piping. The mold cavity is evacuated through the vacuum port of the mold cavity, and the adhesive matrix enters the mold cavity under the action of vacuum and infiltrates the silver-plated nickel mesh. After fully infiltrating the silver-plated nickel mesh, the mold is cooled to obtain a composite film.
对获得的胶膜进行性能测试，该胶膜的体积电阻率为1.6×10 -4Ω·cm，热导率为9W/(m·K)，铝-铝搭接剪切强度为4.5MPa。 The performance test of the obtained adhesive film shows that the volume resistivity of the adhesive film is 1.6×10 -4 Ω·cm, the thermal conductivity is 9W/(m·K), and the Al-Al lap shear strength is 4.5MPa.
对比例Comparative ratio
将环氧树脂胶粘剂加热至90℃并充分搅拌，加入片状银粉并分散均匀，得到胶粘剂基体，其中片状银粉重量为胶粘剂基体总重量的50％。利用胶膜机将胶粘剂基体直接涂布于离型纸上，涂布采用辊压涂布的方式，控制涂布间隙为0.1mm，涂布温度为80℃，涂布速度为1m/min。涂布后待胶膜冷却得到成型的胶膜。The epoxy resin adhesive is heated to 90° C. and fully stirred, and flake silver powder is added and dispersed uniformly to obtain an adhesive matrix, wherein the weight of the flake silver powder is 50% of the total weight of the adhesive matrix. The adhesive matrix was directly coated on the release paper by a film machine, and the coating was carried out by roll coating. The coating gap was controlled to be 0.1 mm, the coating temperature was 80 °C, and the coating speed was 1 m/min. After coating, the film is cooled to obtain a formed film.
对获得的胶膜进行性能测试，该胶膜的体积电阻率为2.5×10 -4Ω·cm，热导率为5.5W/(m·K)，铝-铝搭接剪切强度为12MPa。 The performance test of the obtained adhesive film shows that the volume resistivity of the adhesive film is 2.5×10 -4 Ω·cm, the thermal conductivity is 5.5 W/(m·K), and the Al-Al lap shear strength is 12 MPa.
以上，对本发明的实施方式进行了说明。但是，本发明不限定于上述实施方式。凡在本发明的精神和原则之内，所做的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。The embodiments of the present invention have been described above. However, the present invention is not limited to the above-described embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included within the protection scope of the present invention.

Claims (10)

  1. 一种导电导热胶膜，其特征在于，所述胶膜包括胶粘剂基体和金属网络，所述金属网络嵌入在胶粘剂基体中，所述金属网络的长、宽、高与胶膜的长、宽、高分别相同。A conductive and thermally conductive adhesive film, characterized in that the adhesive film includes an adhesive matrix and a metal network, the metal network is embedded in the adhesive matrix, and the length, width and height of the metal network are related to the length, width, and height of the adhesive film. The heights are the same.
  2. 根据权利要求1所述的胶膜，其特征在于，所述金属网络选自泡沫金属和金属网中的至少一种；The adhesive film according to claim 1, wherein the metal network is selected from at least one of metal foam and metal mesh;
    优选地，所述金属网络为泡沫金属膜时，所述胶粘剂基体充满所述泡沫金属膜的(所有)孔隙；所述金属网络为金属网时，所述胶粘剂基体充满所述金属网的(所有)网孔，并与(所有)金属网丝接触。Preferably, when the metal network is a metal foam film, the adhesive matrix fills (all) pores of the metal foam film; when the metal network is a metal mesh, the adhesive matrix fills (all) the pores of the metal network. ) mesh and in contact with (all) wire mesh.
  3. 根据权利要求2所述的胶膜，其特征在于，所述泡沫金属膜选自泡沫镍、泡沫铜、泡沫银、泡沫铁、泡沫铝、泡沫钛、泡沫铁镍以及表面镀银或镀金的上述泡沫金属膜中的至少一种，优选为泡沫镍、泡沫铜、泡沫银、镀银泡沫镍、和/或镀银泡沫铜；The adhesive film according to claim 2, wherein the foam metal film is selected from the group consisting of nickel foam, copper foam, silver foam, iron foam, aluminum foam, titanium foam, iron-nickel foam and the above-mentioned silver-plated or gold-plated surfaces. at least one of the foamed metal films, preferably nickel foam, copper foam, silver foam, silver-plated nickel foam, and/or silver-plated copper foam;
    优选地，所述泡沫金属膜的孔隙率为50-98％，优选为60-90％；Preferably, the porosity of the foamed metal film is 50-98%, preferably 60-90%;
    优选地，所述金属网选自镍网、铜网、银网、铁网、铝网、钛网、铁镍网以及表面镀银或镀金的上述金属网中的至少一种，优选为镍网、铜网、银网、镀银铜网、和/或镀银镍网；Preferably, the metal mesh is selected from at least one of nickel mesh, copper mesh, silver mesh, iron mesh, aluminum mesh, titanium mesh, iron-nickel mesh and at least one of the above-mentioned metal meshes plated with silver or gold on the surface, preferably nickel mesh , copper mesh, silver mesh, silver-plated copper mesh, and/or silver-plated nickel mesh;
    优选地，所述金属网的网孔目数为40-800目，优选为50-600目；Preferably, the mesh number of the metal mesh is 40-800 mesh, preferably 50-600 mesh;
    优选地，所述金属网选自金属丝编织网、拉伸网、冲孔网和蚀刻网中的至少一种。Preferably, the metal mesh is selected from at least one of metal wire woven mesh, stretched mesh, punched mesh and etched mesh.
  4. 根据权利要求1-3任一项所述的胶膜，其特征在于，所述胶粘剂基体包括热固性胶粘剂和/或热塑性胶粘剂，以及任选含有或不含有的导电和/或导热填料；The adhesive film according to any one of claims 1-3, wherein the adhesive matrix comprises a thermosetting adhesive and/or a thermoplastic adhesive, and optionally an electrically conductive and/or thermally conductive filler;
    优选地，所述热固性胶粘剂选自环氧树脂、酚醛树脂、氰酸酯树脂、不饱和聚酯树脂、双马来酰亚胺树脂、热固性聚酰亚胺树脂和聚苯并恶嗪树脂中的 至少一种；Preferably, the thermosetting adhesive is selected from epoxy resins, phenolic resins, cyanate ester resins, unsaturated polyester resins, bismaleimide resins, thermosetting polyimide resins and polybenzoxazine resins at least one;
    优选地，所述热塑性胶粘剂选自聚乙烯热熔胶、聚丙烯热熔胶、乙烯及其共聚物类热熔胶、聚酯类热熔胶、聚酰胺类热熔胶、聚氨酯类热熔胶、苯乙烯及其嵌段共聚物类热熔胶以及非晶态α-烯烃共聚物(APAO)中的至少一种；优选为聚酰胺(PA)热熔胶和/或乙烯-醋酸乙烯共聚物(EVA)热熔胶；Preferably, the thermoplastic adhesive is selected from polyethylene hot melt adhesive, polypropylene hot melt adhesive, ethylene and its copolymer hot melt adhesive, polyester hot melt adhesive, polyamide hot melt adhesive, and polyurethane hot melt adhesive , at least one of styrene and its block copolymer hot melt adhesive and amorphous α-olefin copolymer (APAO); preferably polyamide (PA) hot melt adhesive and/or ethylene-vinyl acetate copolymer (EVA) hot melt adhesive;
    优选地，所述导电和/或导热填料选自包括片状金属粉、球状金属粉、树枝状金属粉、金纳米线、银纳米线、铜纳米线、石墨、纤维状碳粉、鳞片状碳粉、石墨烯、碳纳米管、金刚石、氧化铝、氧化镁、氧化锌、氧化铍、氧化镍、氧化钙、二氧化硅(结晶型)、氮化铝、氮化硼和碳化硅中的一种或多种；Preferably, the electrically and/or thermally conductive fillers are selected from the group consisting of flake metal powder, spherical metal powder, dendritic metal powder, gold nanowires, silver nanowires, copper nanowires, graphite, fibrous carbon powder, flake carbon powder, graphene, carbon nanotubes, diamond, aluminum oxide, magnesium oxide, zinc oxide, beryllium oxide, nickel oxide, calcium oxide, silicon dioxide (crystalline form), aluminum nitride, boron nitride and silicon carbide one or more;
    优选地，所述导电和/或导热填料的重量占胶粘剂基体重量的0-90％，优选为10-80％。Preferably, the weight of the electrically and/or thermally conductive filler is 0-90% by weight of the adhesive matrix, preferably 10-80%.
  5. 根据权利要求1-4任一项所述的胶膜，其特征在于，所述导电导热胶膜的厚度与所述金属网络的厚度基本相同，优选为0.02-2mm；The adhesive film according to any one of claims 1-4, wherein the thickness of the electrically conductive and thermally conductive adhesive film is substantially the same as the thickness of the metal network, preferably 0.02-2 mm;
    优选地，所述导电导热胶膜包括环氧树脂胶粘剂基体和嵌入其中的镀银泡沫镍，其中镀银泡沫镍的长、宽、高与胶膜整体的长、宽、高分别相同；Preferably, the conductive and thermally conductive adhesive film comprises an epoxy resin adhesive matrix and a silver-plated nickel foam embedded therein, wherein the length, width and height of the silver-plated nickel foam are respectively the same as the overall length, width and height of the adhesive film;
    或者，所述导电导热胶膜包括聚酰胺胶粘剂基体和嵌入其中的镀银铜网，其中镀银铜网的长、宽、高与胶膜整体的长、宽、高分别相同；Alternatively, the conductive and thermally conductive adhesive film includes a polyamide adhesive matrix and a silver-plated copper mesh embedded therein, wherein the length, width and height of the silver-plated copper mesh are respectively the same as the overall length, width and height of the adhesive film;
    或者，所述导电导热胶膜包括含有银粉的不饱和聚酯树脂胶粘剂和嵌入其中的泡沫铜，其中泡沫铜的长、宽、高与胶膜整体的长、宽、高分别相同；Alternatively, the conductive and thermally conductive adhesive film comprises an unsaturated polyester resin adhesive containing silver powder and foamed copper embedded therein, wherein the length, width and height of the foamed copper are respectively the same as the overall length, width and height of the adhesive film;
    或者，所述导电导热胶膜包括含有碳化硅的乙烯-醋酸乙烯共聚物胶粘剂和嵌入其中的镀银镍网，其中镀银镍网的长、宽、高与胶膜整体的长、宽、高分别相同。Alternatively, the conductive and thermally conductive adhesive film includes an ethylene-vinyl acetate copolymer adhesive containing silicon carbide and a silver-plated nickel mesh embedded therein, wherein the length, width and height of the silver-plated nickel mesh are the same as the overall length, width and height of the adhesive film. respectively the same.
  6. 权利要求1-5任一项所述导电导热胶膜的制备方法，其特征在于，所述制备方法包括如下步骤：(a)将所述金属网络压入软化的胶粘剂基体膜中，或者(b)将软化的胶粘剂基体涂覆并渗透至所述金属网络中，或者(c)在辅助压力下将软化的胶粘剂基体填充至所述金属网络中，得到所述导电导热胶膜；The preparation method of the electrically conductive and thermally conductive adhesive film according to any one of claims 1-5, wherein the preparation method comprises the steps of: (a) pressing the metal network into the softened adhesive base film, or (b) pressing the metal network into the softened adhesive base film. ) coating and infiltrating the softened adhesive matrix into the metal network, or (c) filling the softened adhesive matrix into the metal network under auxiliary pressure to obtain the electrically conductive and thermally conductive adhesive film;
    所述胶粘剂基体中任选含有或不含有所述导电和/或导热填料。The electrically and/or thermally conductive filler may or may not be included in the adhesive matrix.
  7. 根据权利要求6所述的制备方法，其特征在于，方案(a)中将软化的胶粘剂基体膜和金属网络叠放，通过热压或压延，使金属网络压入软化的胶粘剂基体膜中；The preparation method according to claim 6, wherein, in the scheme (a), the softened adhesive base film and the metal network are stacked, and the metal network is pressed into the softened adhesive base film by hot pressing or calendering;
    方案(b)中利用胶膜机直接将软化的胶粘剂基体涂布并渗透至金属网络中；In scheme (b), the softened adhesive matrix is directly coated and penetrated into the metal network by a glue film machine;
    方案(c)中所述辅助压力由真空来实现；优选地，熔融的胶粘剂基体在真空作用下浸润所述金属网络。In scheme (c), the auxiliary pressure is achieved by vacuum; preferably, the molten adhesive matrix infiltrates the metal network under the action of vacuum.
  8. 根据权利要求6或7所述的制备方法，其特征在于，当所述胶粘剂基体中含有导电和/或导热填料时，将导电和/或导热填料分散于流动态的胶粘剂中，得到胶粘剂基体。The preparation method according to claim 6 or 7, wherein when the adhesive matrix contains conductive and/or thermally conductive fillers, the conductive and/or thermally conductive fillers are dispersed in the fluidized adhesive to obtain the adhesive matrix.
  9. 权利要求6-8任一项所述方法制备得到的导电导热胶膜。The conductive and thermally conductive adhesive film prepared by the method of any one of claims 6-8.
  10. 权利要求1-5和9任一项所述导电导热胶膜在粘结电子器件和/或电子元件中的应用，实现胶膜两侧被粘接物间的导电和/或导热功能。The application of the electrically conductive and thermally conductive adhesive film described in any one of claims 1 to 5 and 9 in bonding electronic devices and/or electronic components, to achieve the electrical and/or thermal conductivity function between the adherends on both sides of the adhesive film.
PCT/CN2021/102744 2020-06-28 2021-06-28 Electrically and thermally conductive adhesive film and preparation method and application thereof WO2022001952A1 (en)

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