CN113845862A - Conductive and heat-conducting adhesive film and preparation method and application thereof - Google Patents

Conductive and heat-conducting adhesive film and preparation method and application thereof Download PDF

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Publication number
CN113845862A
CN113845862A CN202010599636.8A CN202010599636A CN113845862A CN 113845862 A CN113845862 A CN 113845862A CN 202010599636 A CN202010599636 A CN 202010599636A CN 113845862 A CN113845862 A CN 113845862A
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adhesive
metal
mesh
film
adhesive film
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CN113845862B (en
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黄贵文
肖红梅
刘玉
渠成兵
李娜
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Technical Institute of Physics and Chemistry of CAS
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Technical Institute of Physics and Chemistry of CAS
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Priority to PCT/CN2021/102744 priority 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

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physics & Mathematics (AREA)
  • Dispersion Chemistry (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Adhesive Tapes (AREA)

Abstract

The invention discloses an electrically and thermally conductive adhesive film, and a preparation method and application thereof. The adhesive film comprises an adhesive matrix and a metal network, wherein the metal network is embedded in the adhesive matrix, and the length, width and height of the metal network are the same as the length, width and height of the whole adhesive film. The adhesive film is used for bonding objects to be bonded on two sides and realizes the functions of electric conduction, heat conduction and the like. Because the continuous metal network is used for replacing the traditional microcosmic lapped electric and heat conducting filler, the adhesive film can obtain higher electric conductivity and heat conductivity, reduce the volume content of the filler and obtain high bonding strength. Meanwhile, the structural consistency of the adhesive film can be ensured by utilizing the continuous metal network, so that the functional adhesive film with good performance consistency is obtained.

Description

Conductive and heat-conducting adhesive film and preparation method and application thereof
Technical Field
The invention belongs to the technical field of material functional bonding, and particularly relates to an electric and heat conducting adhesive film, and a preparation method and application thereof.
Background
Adhesive bonding is an important technical means for joining two material parts in engineering applications. In practical applications, the adhesion of some components requires not only the adhesive layer to provide mechanical connection, but also some special functions. For example, some electronic devices require an adhesive layer to provide good electrical conductivity, and some components requiring heat dissipation during operation require a heat sink to have a good thermal conductivity. The functionalized adhesive is needed, and has mechanical bonding performance and functions of electric conduction, heat conduction and the like. To achieve this goal, it is common to add a microscopically electrically and thermally conductive filler to the adhesive matrix to achieve a certain percolation threshold, thereby obtaining a functionalized adhesive.
In the application process, the traditional adhesive needs to glue the surface of the bonded object, and then the bonded object is pressed for bonding. The sizing process, however, may result in uneven or variable sizing of the bondline due to operational variances, resulting in inconsistent bonding performance in batch part bonding. Based on this problem, adhesives in the form of a film were developed. The adhesive film is an adhesive which is prefabricated into a uniform film state and is in a solid state or a gel state at an operation temperature. When in use, the adhesive film is directly placed on the interface between the bonded objects for pressing and curing without gluing. The adhesive film can conveniently provide a uniform and quantitative adhesive layer so as to obtain an adhesive interface with good consistency. And the adhesive film can be cut at will and is suitable for bonding of bonding surfaces in different shapes. Therefore, the adhesive in the form of the adhesive film has outstanding advantages in practical engineering application.
The adhesive film is generally prepared by heating a thermosetting or thermoplastic adhesive to a temperature above the softening temperature and uniformly coating the adhesive on a release layer. For the functional adhesive film with electric and heat conductivity, the functional adhesive film is generally obtained by fully mixing microscopic electric and heat conductive fillers with an adhesive matrix and then coating the mixture. However, the adhesive matrix of the adhesive film generally has high viscosity, so that the process difficulty is high when the microscopic filler and the adhesive matrix are mixed above the softening temperature, and the problems of filler agglomeration, uneven distribution and the like easily occur in the composite adhesive film obtained by coating, so that the performance of the adhesive film is unstable.
Disclosure of Invention
The invention provides an electric conduction and heat conduction adhesive film which comprises an adhesive matrix and a metal network, wherein the metal network is embedded in the adhesive matrix, and the length, the width and the height of the metal network are respectively the same as those of the adhesive film.
According to an embodiment of the invention, the metal network is at least one of a metal foam and a metal mesh, for example the metal network is a metal foam film or a metal mesh.
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.
According to an embodiment of the invention, when the metal network is a metal mesh, the adhesive matrix fills (all) of the mesh openings of the metal mesh and is in contact with (all) of the metal mesh wires.
According to an embodiment of the present invention, the metal foam film is selected from at least one of nickel foam, copper foam, silver foam, iron foam, aluminum foam, titanium foam, iron nickel foam, and the metal foam film with silver or gold plated on the surface, such as nickel foam, copper foam, silver plated nickel foam, and/or silver plated copper foam.
According to an embodiment of the invention, the thickness of the foamed metal film is 0.02-2mm, for example 0.05-0.15mm, exemplary 0.1mm, 0.15mm, 0.2 mm.
According to an embodiment of the invention, the porosity of the foamed metal film is 50-98%, such as 60-90%, exemplary 60%, 70%, 80%, 90%, 95%.
According to an embodiment of the present invention, the metal mesh is selected from a nickel mesh, a copper mesh, a silver mesh, an iron mesh, an aluminum mesh, a titanium mesh, an iron-nickel mesh, and at least one of the above metal meshes surface-plated with silver or gold, such as a nickel mesh, a copper mesh, a silver-plated copper mesh, and/or a silver-plated nickel mesh.
According to an embodiment of the invention, the metal mesh has a thickness of 0.02-2mm, for example a thickness of 0.05-0.15mm, exemplary 0.1mm, 0.15mm, 0.2 mm.
According to an embodiment of the invention, the mesh size of the metal mesh is 40-800 mesh, such as 50-600 mesh, exemplary 100 mesh, 200 mesh, 300 mesh.
According to an embodiment of the present invention, the metal mesh may be at least one of a woven wire mesh, a stretched wire mesh, a punched wire mesh, an etched wire mesh, and the like.
According to the embodiment of the present invention, the electrically and thermally conductive adhesive film may contain the same or different metal networks stacked together. For example, two layers of nickel mesh or a layer of nickel mesh and a layer of copper mesh are overlapped together, and the thickness of the copper mesh is the same as that of the adhesive film.
According to an embodiment of the invention, the adhesive matrix comprises a thermosetting adhesive and/or a thermoplastic adhesive, and optionally an electrically and/or thermally conductive filler, with or without. The present invention utilizes a continuous metal network structure to reduce the weight content of electrically and/or thermally conductive fillers, thereby achieving high bond strength.
According to an embodiment of the present invention, the thermosetting adhesive is at least one of an epoxy resin, a phenol resin, a cyanate resin, an unsaturated polyester resin, a bismaleimide resin, a thermosetting polyimide resin, and a polybenzoxazine resin. For example epoxy resins and/or unsaturated polyester resins.
According to an embodiment of the present invention, the thermoplastic adhesive is at least one of a polyethylene hot melt adhesive, a polypropylene hot melt adhesive, an ethylene and its copolymer hot melt adhesive, a polyester hot melt adhesive, a polyamide hot melt adhesive, a polyurethane hot melt adhesive, a styrene and its block copolymer hot melt adhesive, and an amorphous α -olefin copolymer (APAO). For example, Polyamide (PA) hot melt adhesives and/or Ethylene Vinyl Acetate (EVA) hot melt adhesives.
According to an embodiment of the present invention, the electrically and/or thermally conductive filler includes one or more of flake metal powder, spherical metal powder, dendritic metal powder, gold nanowire, silver nanowire, copper nanowire, graphite, fibrous carbon powder, scale-like carbon powder, graphene, carbon nanotube, diamond, alumina, magnesium oxide, zinc oxide, beryllium oxide, nickel oxide, calcium oxide, silica (crystalline), aluminum nitride, boron nitride, and silicon carbide.
According to an embodiment of the invention, the electrically and/or thermally conductive filler is present in an amount of 0-90%, such as 10-80%, e.g. 20-50%, exemplary 0, 10%, 20%, 30%, 40%, 50% by weight of the adhesive matrix.
According to an embodiment of the invention, the electrically and thermally conductive adhesive film has a thickness substantially the same as the thickness of the continuous metal network, for example 0.02-2mm, for example 0.05-0.15mm, exemplarily 0.1mm, 0.15mm, 0.2 mm.
According to the embodiment of the invention, the volume resistivity of the conductive and heat-conducting adhesive film is less than 5.0 x 10-4Omega. cm, preferably (1.1-2.5). times.10-4Ω · cm, exemplary 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 thermal conductivity of the electrically and thermally conductive adhesive film is greater than 6W/(m · K), preferably 8-20W/(m · K), exemplary 8W/(m · K), 9W/(m · K), 10W/(m · K), 10.5W/(m · K).
According to an exemplary aspect of the present invention, the electrically and thermally conductive adhesive film includes an epoxy adhesive matrix and silver-plated nickel foam embedded therein, wherein the length, width, and height of the silver-plated nickel foam are respectively the same as the length, width, and height of the adhesive film as a whole.
According to an exemplary aspect of the present invention, the electrically 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 length, width, and height of the adhesive film as a whole.
According to an exemplary aspect of the present invention, the electrically and thermally conductive adhesive film includes an unsaturated polyester resin adhesive containing silver powder and a copper foam embedded therein, wherein the length, width and height of the copper foam are respectively the same as the length, width and height of the adhesive film as a whole.
According to an exemplary aspect of the present invention, the electrically 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 respectively the same as the length, width, and height of the adhesive film as a whole.
The invention also provides a preparation method of the conductive and heat-conducting adhesive film, which comprises the following steps: (a) pressing the metal network into a softened adhesive matrix film, or (b) coating and penetrating 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 conductive and heat-conductive adhesive film;
according to the embodiment of the invention, in the method, the adhesive matrix and the metal network are compounded, and the conductive and heat-conducting adhesive film is obtained after cooling.
The adhesive matrix optionally contains or does not contain the electrically and/or thermally conductive filler.
According to an embodiment of the present invention, embodiment (a) comprises prefabricating the adhesive matrix into an adhesive matrix film. Preferably, the thickness of the adhesive matrix film is the same as the thickness of the metal network.
The pressing in embodiment (a) may be performed by pressing the metal network into the adhesive matrix film using a flat press, a roll calender or the like, according to an embodiment of the present invention.
According to an embodiment of the present invention, in the scheme (a), the pressing may be hot pressing or calendering.
According to an embodiment of the invention, in variant (a), the hot pressing temperature is between 80 and 150 ℃, such as between 90 and 130 ℃, exemplarily 100 ℃, 110 ℃, 120 ℃. Wherein the pressure of the hot pressing is 3-10MPa, such as 4-8MPa, exemplary 5MPa, 6MPa, 7 MPa. Wherein the dwell time of the hot pressing is 0.5 to 2 minutes, for example 1 minute.
According to an embodiment of the invention, in variant (a), the temperature of the calendering is between 80 and 150 ℃, such as between 90 and 130 ℃, exemplarily between 100 ℃, 110 ℃, 120 ℃. Wherein the gap between the calendering rolls during calendering is 0.1 to 0.3mm, such as 0.15 to 0.25mm, exemplary 0.2 mm. Wherein the calendering speed is 0.2 to 1m/min, such as 0.4 to 0.8m/min, exemplary 0.5 m/min.
According to an embodiment of the present invention, the softened adhesive matrix film and the metal network are stacked in scheme (a), and the metal network is pressed into the softened adhesive matrix film by hot pressing or calendering.
According to an embodiment of the present invention, the softened adhesive matrix may be directly coated and infiltrated into the metal network in the embodiment (b) by using a film coating machine or the like.
According to an embodiment of the present invention, in scheme (b), the manner of coating is a coating manner known in the art, such as roll coating. Wherein the coating gap is 0.05-0.3mm, such as 0.15-0.25mm, exemplary 0.15 mm. Where the temperature of the coating is 80-150 deg.C, such as 90-130 deg.C, exemplary 90 deg.C, 100 deg.C, 110 deg.C, 120 deg.C. Wherein the coating speed is 0.5-2m/min, such as 0.7-1.5m/min, exemplary 1 m/min.
According to an embodiment of the present invention, the auxiliary pressure in the embodiment (c) may be achieved by an auxiliary means such as vacuum. For example, a molten adhesive matrix is subjected to a vacuum to impregnate the metal network.
According to an embodiment of the present invention, when the adhesive matrix contains the electrically and/or thermally conductive filler, the electrically and/or thermally conductive filler may be dispersed in the adhesive in a flowing state to obtain the adhesive matrix.
The invention also provides the conductive and heat-conducting adhesive film prepared by the method.
The invention also provides application of the conductive and heat-conducting adhesive film in bonding electronic devices and/or electronic elements so as to realize the conductive and/or heat-conducting function between bonded objects on two sides of the adhesive film. Preferably, when bonding, the conductive and heat-conducting adhesive film is directly contacted with the bonded objects on two sides.
The invention has the beneficial effects that:
the invention provides an electric conduction and heat conduction adhesive film with a novel structure. The adhesive film utilizes a continuous metal network to replace the traditional microcosmic electric and heat conducting filler, so that on one hand, the forming process of the adhesive film can be simplified, and higher electric conductivity and heat conductivity can be obtained; on the other hand, the use of a continuous metal network allows to reduce the filler weight content to a certain extent, thus obtaining a higher bonding strength. Moreover, the continuous metal network can ensure the consistency of the structure of the adhesive film, and the functional adhesive film with good performance consistency is obtained. Meanwhile, the adhesive film has high electric conduction, heat conduction and bonding properties. The method comprises the following specific steps:
1) high electrical and thermal conductivity can be achieved by using a continuous metal network structure;
2) the continuous metal network structure is filled in the directions of the length, the width and the height of the adhesive film and is directly contacted with the adhered objects on two sides in the use process, so that the interface resistance and the thermal resistance can be reduced;
3) the weight content of the filler can be reduced by utilizing a continuous metal network structure, so that high bonding strength is obtained;
4) the consistency of the performance of the adhesive film can be ensured by utilizing a continuous metal network structure.
Drawings
FIG. 1 is a schematic cross-sectional view of a film prepared by using a foamed metal thin 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.
Detailed Description
The technical solution of the present invention will be further described in detail with reference to specific embodiments. It is to be understood that the following examples are only illustrative and explanatory of the present invention and should not be construed as limiting the scope of the present invention. All the technologies realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.
Unless otherwise indicated, the raw materials and reagents used in the following examples are all commercially available products or can be prepared by known methods.
The volume resistivity of the adhesive films in the examples was tested according to ISO16525, the thermal conductivity according to ASTM E1461 and the shear strength according to ISO-4587: 2003.
Example 1
In this example, a flat press was used for film formation.
Heating the epoxy resin adhesive to a temperature higher than the softening temperature, and coating the epoxy resin adhesive on release paper by using a coating machine to prepare an epoxy resin adhesive film with the thickness of 0.1mm, wherein the coating temperature is 110 ℃. After the adhesive film was cooled, it was cut into a film having a size of 20cm × 30 cm.
Silver plated nickel foam with a thickness of 0.1mm and a porosity of 90% was also cut into a 20cm x 30cm film. The silver plating amount of the silver-plated foam nickel was 10% by weight of the nickel.
The silver-plated foamed nickel and the epoxy resin adhesive film are adhered together, placed between two pieces of release paper, placed between an upper flat plate and a lower flat plate of a flat plate press machine, and subjected to hot pressing. The hot pressing temperature is 100 ℃, the pressure is 5MPa, and the pressure maintaining time is 1 minute. Under the action of pressure, the epoxy resin above the softening temperature permeates into the pores of the silver-plated foamed nickel, and because the foamed metal has certain pressure resistance, redundant resin overflows from the side edge, and finally a composite adhesive film with the same thickness as the silver-plated foamed nickel is formed, wherein the section structure of the composite adhesive film is shown in figure 1.
The obtained adhesive film was subjected to a performance test, and the volume resistivity of the adhesive film was 1.8X 10-4Omega cm, thermal conductivity of 8W/(m.K), and aluminum-aluminum lap shear strength of 23 MPa.
Example 2
In this example, a roll calender was used for film formation.
Heating Polyamide (PA) adhesive to a temperature higher than softening temperature, coating the PA adhesive on release paper by using a coating machine, and rolling to prepare an adhesive matrix adhesive film with the thickness of 0.15mm and the width of 30cm, wherein the coating temperature is 140 ℃.
The silver-plated copper mesh with the thickness of 0.2mm, the mesh number of 300 meshes and the width of 30cm is compounded with the adhesive matrix adhesive film, then placed between an upper layer of release paper and a lower layer of release paper, the thickness of the release paper is 0.1mm, and the release paper is fed into a double-roller calender through an unreeling device for continuous hot calendering. The gap between the calendering rolls is controlled to be 0.4mm, the temperature of the calendering rolls is controlled to be 130 ℃, and the calendering speed is controlled to be 0.5 m/min. After the rolling, the glue film is cooled and rolled to obtain a continuously produced composite glue film with the thickness of 0.2mm, and the section structure of the composite glue film is shown in figure 2.
The obtained adhesive film was subjected to a performance test, and the volume resistivity of the adhesive film was 1.5X 10-4Omega cm, thermal conductivity of 10W/(m.K), and aluminum-aluminum lap shear strength of 6 MPa.
Example 3
In this embodiment, a film forming machine is used to perform film forming.
The copper foam with a thickness of 0.15mm and a porosity of 85% was placed on a layer of release paper. Heating the unsaturated polyester resin adhesive to 90 ℃, fully stirring, adding the flake silver powder, and uniformly dispersing to obtain an adhesive matrix, wherein the weight of the flake silver powder is 30% of the total weight of the adhesive matrix. The adhesive matrix is directly coated on the foam copper by using an adhesive film machine, a rolling coating mode is adopted for coating, the coating gap is controlled to be 0.15mm, the coating temperature is 90 ℃, and the coating speed is 1 m/min. And after coating, cooling the glue film to obtain the formed composite glue film.
The obtained adhesive film was subjected to a performance test, and the volume resistivity of the adhesive film was 1.2X 10-4Omega cm, thermal conductivity of 10.5W/(m.K), and gold-gold lap shear strength of 24 MPa.
Example 4
In this embodiment, a vacuum assisted resin transfer molding method is used for film molding.
The silver-plated nickel screen with the thickness of 0.15mm and the mesh number of 200 meshes is cut into a film with the thickness of 30cm multiplied by 40 cm. Two nickel mesh films are overlapped and placed between an upper release paper and a lower release paper, and the thickness of the release paper is 0.1 mm. And (3) putting the stacked nickel mesh and release paper into a flat plate die cavity formed by vacuum assistance, preheating the die to 120 ℃, and setting the distance between an upper flat plate and a lower flat plate of the die cavity to be 0.5 mm.
Heating ethylene-vinyl acetate copolymer (EVA) hot melt adhesive to 120 ℃ in another container to enable the EVA hot melt adhesive to be in a flowable state, adding silicon carbide powder and uniformly dispersing to obtain an adhesive matrix, wherein the weight of the silicon carbide is 30% of the total weight of the adhesive matrix. The molten adhesive matrix is connected to the mold cavity by a conduit. And (3) vacuumizing the die cavity through a vacuum port of the die cavity, so that the adhesive matrix enters the die cavity under the vacuum action and is soaked in the silver-plated nickel net. And after the silver-plated nickel mesh is fully soaked, cooling the mould to obtain the composite adhesive film.
The obtained adhesive film was subjected to a performance test, and the volume resistivity of the adhesive film was 1.6X 10-4Omega cm, thermal conductivity of 9W/(m.K), and aluminum-aluminum lap shear strength of 4.5 MPa.
Comparative example
Heating the epoxy resin adhesive to 90 ℃, fully stirring, adding the flake silver powder, and uniformly dispersing 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 is directly coated on release paper by using an adhesive film machine, a rolling coating mode is adopted for coating, the coating gap is controlled to be 0.1mm, the coating temperature is 80 ℃, and the coating speed is 1 m/min. And after coating, cooling the adhesive film to obtain a formed adhesive film.
The obtained adhesive film was subjected to a performance test, and the volume resistivity of the adhesive film was 2.5X 10-4Omega cm, thermal conductivity of 5.5W/(m.K), and aluminum-aluminum lap shear strength of 12 MPa.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. The electric conduction and heat conduction adhesive film is characterized by comprising an adhesive matrix and a metal network, wherein the metal network is embedded in the adhesive matrix, and the length, width and height of the metal network are respectively the same as those of the adhesive film.
2. The glue film of claim 1, wherein the metal network is at least one of a metal foam and a metal mesh, for example the metal network is a metal foam film or a metal mesh.
Preferably, when the metal network is a metal foam film, the adhesive matrix fills (all) of the pores of the metal foam film.
Preferably, when the metal network is a metal mesh, the adhesive matrix fills (all) of the mesh openings of the metal mesh and contacts (all) of the metal mesh wires.
3. The adhesive film according to claim 2, wherein the foamed metal film is selected from at least one of foamed nickel, foamed copper, foamed silver, foamed iron, foamed aluminum, foamed titanium, foamed iron nickel and the above foamed metal film with silver or gold plated surface, preferably foamed nickel, foamed copper, foamed silver, silver-plated foamed nickel and/or silver-plated foamed copper.
Preferably, the porosity of the foamed metal film is 50-98%, preferably 60-90%.
Preferably, the metal mesh is selected from nickel mesh, copper mesh, silver mesh, iron mesh, aluminum mesh, titanium mesh, iron-nickel mesh and at least one of the metal meshes with silver or gold plated on the surface, preferably nickel mesh, copper mesh, silver-plated copper mesh, and/or silver-plated nickel mesh.
Preferably, the mesh number of the metal net is 40-800 meshes, preferably 50-600 meshes.
Preferably, the metal mesh is at least one of a woven wire mesh, a stretched wire mesh, a punched wire mesh and an etched wire mesh.
4. Adhesive film according to any one of claims 1 to 3, wherein the adhesive matrix comprises a thermosetting adhesive and/or a thermoplastic adhesive, and optionally an electrically and/or thermally conductive filler, with or without.
Preferably, the thermosetting adhesive is at least one of epoxy resin, phenolic resin, cyanate ester resin, unsaturated polyester resin, bismaleimide resin, thermosetting polyimide resin and polybenzoxazine resin; preferably an epoxy resin and/or an unsaturated polyester resin.
Preferably, the thermoplastic adhesive is at least one of 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, styrene and its block copolymer hot melt adhesive, and amorphous alpha-olefin copolymer (APAO); preferably a Polyamide (PA) hot melt adhesive and/or an ethylene vinyl acetate copolymer (EVA) hot melt adhesive.
Preferably, the electrically and/or thermally conductive filler includes one or more of flake metal powder, spherical metal powder, dendritic metal powder, gold nanowire, silver nanowire, copper nanowire, graphite, fibrous carbon powder, flaky carbon powder, graphene, carbon nanotube, diamond, alumina, magnesium oxide, zinc oxide, beryllium oxide, nickel oxide, calcium oxide, silica (crystalline), aluminum nitride, boron nitride, and silicon carbide.
Preferably, the electrically and/or thermally conductive filler is present in an amount of 0 to 90%, preferably 10 to 80%, more preferably 20 to 50% by weight of the adhesive matrix.
5. The adhesive film according to any one of claims 1 to 4, wherein the thickness of the electrically and thermally conductive adhesive film is substantially the same as the thickness of the metal network, preferably 0.02 to 2 mm.
Preferably, the electrically and thermally conductive adhesive film comprises an epoxy resin adhesive matrix and silver-plated nickel foam embedded therein, wherein the length, width and height of the silver-plated nickel foam are respectively the same as the length, width and height of the adhesive film.
Preferably, the electrically and thermally conductive adhesive film comprises 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 length, width and height of the whole adhesive film.
Preferably, the conductive and heat-conducting adhesive film comprises an unsaturated polyester resin adhesive containing silver powder and foam copper embedded in the adhesive film, wherein the length, width and height of the foam copper are respectively the same as the length, width and height of the whole adhesive film.
Preferably, the conductive and heat-conducting adhesive film comprises an ethylene-vinyl acetate copolymer adhesive containing silicon carbide and a silver-plated nickel net embedded in the ethylene-vinyl acetate copolymer adhesive, wherein the length, the width and the height of the silver-plated nickel net are respectively the same as the length, the width and the height of the whole adhesive film.
6. The method for preparing the electrically and thermally conductive adhesive film according to any one of claims 1 to 5, wherein the method comprises the following steps: (a) pressing the metal network into a softened adhesive matrix film, or (b) coating and penetrating 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 conductive and heat-conductive adhesive film;
the adhesive matrix optionally contains or does not contain the electrically and/or thermally conductive filler.
7. The method of claim 6, wherein the step (a) comprises prefabricating the adhesive matrix into an adhesive matrix film.
Preferably, in the scheme (a), the pressing is hot pressing or calendering.
Preferably, the softened adhesive matrix film and the metal network are stacked in scheme (a), and the metal network is pressed into the softened adhesive matrix film by hot pressing or calendering.
Preferably, the softened adhesive matrix is directly coated and impregnated into the metal network in the scheme (b) by using a film coating machine.
Preferably, in the scheme (b), the coating is roll coating.
Preferably, the auxiliary pressure in option (c) is achieved by vacuum; preferably, the molten adhesive matrix impregnates the metal network under vacuum.
8. The production method according to claim 6 or 7, characterized in that, when the adhesive matrix contains an electrically and/or thermally conductive filler, the electrically and/or thermally conductive filler is dispersed in the adhesive in a flowing state to obtain the adhesive matrix.
9. The electrically and thermally conductive adhesive film prepared by the method of any one of claims 6 to 8.
10. Use of the electrically and thermally conductive adhesive film of any one of claims 1 to 5 and 9 for bonding electronic devices and/or electronic components, to achieve the electrical and/or thermal conductivity between the two substrates on both sides of the adhesive film.
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