CN114286581A - Composite heat dissipation film and preparation method thereof - Google Patents
Composite heat dissipation film and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a composite heat dissipation film and a manufacturing method thereof. According to the composite heat dissipation film, the graphene sheet and the metal layer are used for heat dissipation, and the metal layer is subjected to treatment by methods such as vapor physical deposition, plasma, chemical etching, chemical plating and the like, so that the surface of the metal layer is made to be a protruding structure, the original smooth metal surface is rough, the original smooth planar structure is changed into a three-dimensional 3D rough structure, the protruding structure can be embedded into the graphene heat conduction layer, the metal layer and the graphene layer are better embedded, the heat dissipation effect and the shielding function are greatly improved while the combination is tight. The composite heat dissipation film organically integrates heat dissipation and shielding, so that the manufactured product has high heat dissipation performance and shielding function, and is suitable for the aspects or fields of heat dissipation, electromagnetic shielding, copper-clad plates, Flexible Printed Circuit (FPC), display, communication and the like.
Description
Technical Field
The invention belongs to the fields of display, electronic components and communication, and relates to a heat dissipation film, in particular to a composite heat dissipation film for 5G communication and electronic components, which is used as a functional film for conductive adhesive films, FPCs (flexible printed circuits), displays and the like.
Background
The rapid development of information technology has led to significant increase in chip power consumption of electronic components, and heat dissipation has become an important part of the electronic components. The development of a heat dissipation film with high heat conductivity is an effective means for realizing high-efficiency heat dissipation under the conditions of integration, high density and miniaturization of electronic equipment and instruments. The current internal heat dissipation mode of the mobile phone mainly uses graphite sheet heat dissipation. The artificial graphite flake heat dissipation film is an artificial graphite flake film formed by carbonizing and graphitizing a Polyimide (PI) film at high temperature, and although the heat conducting property in the XY direction is excellent, the heat conducting property in the Z direction (longitudinal direction) is poor, the shielding effect is not ideal, and the requirement of high-frequency and high-speed transmission shielding of electromagnetic waves in the 5G era cannot be met.
At present, the main way to solve the problem of insufficient heat dissipation in the Z direction (longitudinal direction) of graphite is to stack graphite materials and metal materials to prepare composite materials. For example, the patent application with publication number CN 109334155A, CN 110283551A, CN 106079693 a, the utility model patents published as CN 209643237U, CN 208218753U, CN 207172907U, CN 205033658U, CN 204466141U, CN 207310703U and CN 208292912U all directly use the metal materials such as ready-made copper foil or aluminum foil, or the like, or the laminating or bonding method to stack them, the existing stacking method directly using ready-made metal foil is limited by the thickness of the metal foil (at least 5 μm), and cannot be made into ultra-thin heat dissipation film, so it is difficult to meet the requirements of thin, dense and thin fine circuit; although the utility model CN 205510635U, CN 206870511U adopts the chemical vapor deposition method to deposit the graphene material on the surface of the metal foil, an ultra-thin heat dissipation film can be prepared, but the thickness of the heat dissipation layer is insufficient, the heat flux is small, the heat dissipation effect is unknown, and the bonding force between the graphene and the metal foil is not guaranteed; while patent numbers CN 206350292U and CN 206349356U only describe structural design, no specific manufacturing method is given; patent No. CN 110718516 a uses a 3D word at the same time as the present invention, but the 3D structure thereof refers to the morphology of the graphene film, and is different from the 3D concept of the present invention.
The graphene sheet is used for compounding the 3D structure metal layer, the gas phase physical deposition (PVD) technology and the precision compounding technology are adopted, the composite heat dissipation shielding film with the high heat dissipation function and the excellent shielding function is prepared, the thickness can be realized from 25 micrometers to 400 micrometers, and the metal layer and the heat dissipation layer are tightly and firmly combined. As an original integrated functional film, the composite heat dissipation shielding film has high heat dissipation efficiency and excellent shielding function.
Disclosure of Invention
The invention aims to improve the heat dissipation performance of the existing heat dissipation film, solve the technical problems of poor heat conduction and poor heat dissipation effect of graphite and graphene sheets in the Z direction (longitudinal direction), and provide a composite heat dissipation shielding film integrating heat dissipation and shielding functions; the heat dissipation film layer and the 3D structure metal layer are reasonably superposed; meanwhile, the composite heat dissipation film with the 3D metal structure layer prepared by the method is simple, convenient, light and thin, convenient to use, capable of being produced in batches and suitable for various electronic products and communication equipment; the composite heat dissipation shielding film is made of the heat dissipation layer and the 3D structure metal layer, and effectively solves the problems that the existing heat dissipation film is poor in Z-direction heat dissipation and insufficient in shielding function.
In order to achieve the object of the present invention, in one aspect, the present invention provides a composite heat dissipation film having a 3D structure metal layer, which includes a heat conduction layer, a heat conduction adhesion layer, a 3D structure metal layer, a heat conduction adhesive layer, and a protection film layer, which are closely stacked in sequence.
The heat conduction layer is a graphene sheet layer, a graphite sheet layer or a film layer made of a heat conduction coating containing graphene or high-heat-conductivity carbon nanotubes, and is preferably a graphene sheet layer.
In particular, the thickness of the heat conducting layer is 5 to 300 μm, preferably 17 to 100 μm, and more preferably 17 μm.
Wherein the surface of the heat conduction adhesion layer is uneven; has three-dimensional irregular surface topography. Granular heat conduction particles are contained in the heat conduction adhesion layer, and the heat conduction particles cause the surface of the heat conduction adhesion layer to be uneven and have an irregular three-dimensional surface structure.
Particularly, the heat conduction adhesion layer is formed by coating heat conduction adhesion slurry on the surface of the heat conduction layer and drying, wherein the heat conduction adhesion slurry comprises adhesion layer resin, heat conduction particles and adhesion layer diluent.
In particular, the thickness of the thermally conductive adhesive layer is 5 to 20 μm, preferably 10 μm.
Wherein, the resin of the adhesion layer is epoxy resin, acrylic resin, polyurethane resin, polyester resin or modified resin thereof, preferably acrylic resin; the heat conducting particles are one or more of graphene, aluminum oxide, silicon nitride or carbon nanotubes, and preferably are aluminum oxide and graphene; the adhesive layer thinner is one or more of water, butanone, acetone, ethyl acetate, butyl acetate or propylene glycol methyl ether acetate (PMA).
In particular, the thermally conductive particles have a particle size of 5 to 20 μm, preferably 10 μm. The heat conducting particles are in a particle state, and after coating and drying, an uneven three-dimensional (namely 3D) surface structure form is formed on the surface of the graphene sheet of the heat conducting layer.
Particularly, the weight ratio of the resin of the bonding layer and the heat conducting particles in the heat conducting bonding layer is (30-90): (10-70), preferably (30-80): (15-70), and more preferably 60: 25.
Particularly, the resin of the bonding layer in the heat-conducting bonding layer is acrylic resin; the heat conducting particles are aluminum oxide and graphene.
Particularly, the weight parts of acrylic resin, alumina and graphene in the heat conduction adhesion layer are as follows: acrylic resin 60: 20, alumina: and (5) graphene.
Particularly, the weight ratio of the aluminum oxide to the graphene in the heat conducting particles is (3-5):1, and preferably 4: 1.
In particular, the coating method of the heat-conductive adhesive slurry includes knife coating, screen roller, dimple, slit, doctor blade, roller coating, screen, coating, roller pressing, spray coating, etc., and the dimple coating method is preferable.
And drying the heat-conducting adhesive slurry on the surface of the heat-conducting layer to prepare the heat-conducting adhesive layer with a three-dimensional surface structure or a concave-convex irregular surface structure.
The heat-conducting adhesion layer is a film layer formed by coating heat-conducting adhesion slurry on the surface of the heat-conducting layer and drying the heat-conducting adhesion slurry.
The heat-conducting adhesive layer can also adopt heat-conducting adhesive or a double-sided adhesive layer, and an irregular three-dimensional structure is pressed on the surface of the heat-conducting adhesive or the double-sided adhesive layer in a roller and rolling mode to form the heat-conducting adhesive layer with uneven surface and three-dimensional surface appearance. The heat conducting glue and/or the double-sided adhesive tape adopt the heat conducting glue and/or the double-sided adhesive tape materials which are known in the field.
The metal of the 3D structure metal layer is selected from one or an alloy of any two of gold, silver, copper, nickel and aluminum, preferably gold, silver, copper, nickel, aluminum, nickel silver and nickel copper, and more preferably copper.
In particular, the thickness of the 3D structure metal layer is 1-100 mu m.
Particularly, the 3D structure metal layer is a metal film with an uneven surface, the surface of the metal film is uneven, and the metal film has a three-dimensional irregular three-dimensional appearance. The 3D structure metal layer has the same surface appearance as the heat conduction adhesion layer.
Particularly, the 3D structure metal layer includes a base metal layer and a thickened metal layer, wherein the base metal layer is formed on the surface of the heat conductive adhesive layer having a three-dimensional surface structure or a concave-convex irregular surface structure, the surface structure of the heat conductive adhesive layer is maintained, and the surface of the base metal layer is thickened to maintain the surface structure of the base metal layer.
In particular, the base metal layer is realized by adopting a vacuum coating mode, and the thickness of the base metal layer is 0.05-0.5 μm, and preferably 0.1-0.3 μm. The thickened metal layer is realized by adopting a chemical plating mode, and the thickness of the thickened metal layer is 1-20 mu m, preferably 8-20 mu m.
The base metal layer is deposited on the surface of the heat conduction adhesion layer in a vacuum plating mode, the surface of the base metal layer is in a three-dimensional surface structure or a concave-convex irregular surface structure because heat conduction particles in the heat conduction adhesion layer are in a particle state, and the base metal layer deposited on the surface of the heat conduction adhesion layer by a vacuum coating method also has a three-dimensional structure; the thickened metal layer is formed by depositing metal on the surface of the base metal layer by a chemical plating method, a peak effect can be generated, the speed of depositing the metal at the convex part and the concave part of the uneven surface is different, and the convex part is deposited faster than the concave part, so that the surface of the originally concave-convex heat-conducting adhesion layer is more convex after the electroplating deposition, and the peak shape is grown.
The 3D structure metal layer is prepared by the following method: and forming a metal film layer with a three-dimensional structure layer or an irregular three-dimensional surface structure on the surface of the heat conduction adhesion layer by sequentially adopting a vacuum coating method and a chemical plating method.
Particularly, a vacuum coating method is adopted to form a basic metal layer with a three-dimensional structure layer or an irregular three-dimensional surface structure on the surface of the heat conduction adhesion layer; and forming a thickened metal layer with a three-dimensional structure layer or an irregular three-dimensional surface structure on the surface of the base metal layer by adopting a chemical plating method.
Wherein the vacuum coating method is vacuum evaporation plating, magnetron sputtering plating, vacuum ion plating or vacuum beam deposition, and is preferably magnetron sputtering plating; the chemical plating is selected from alkaline plating or acid plating, and acid plating is preferred.
Particularly, the magnetron sputtering is realized by adopting a common power supply or a radio frequency power supply, and preferably adopts the radio frequency power supply.
In particular, the vacuum degree is controlled to be 10 in the magnetron sputtering process-1—10-5Pa, current 5-30A.
In particular, the chemical acid plating process comprises the following steps: CuSO4 70-90g/l；H2SO4180-220 g/l; HCl 40-80 ppm; 5-15ml/l of copper plating additive SCC-100-2B; the temperature is 20-24 ℃; the cathode current density is 10-40 ASF. And controlling the thickness of the plated film according to parameters such as current and the like.
The thickness of the 3D structure metal layer prepared by adopting a vacuum coating method and a chemical plating method is 1-20 mu m; the thickness of the 3D structure metal layer manufactured by adopting a chemical etching method is 12-100 mu m.
Chemical etching is carried out on the surface of the existing metal foil to form a three-dimensional metal surface structure or an irregular three-dimensional surface structure and a micropore-shaped layer.
Wherein, another preparation method of the 3D structure metal layer comprises the following steps: chemical etching treatment is carried out on the surface of the existing metal foil to form a film layer with an irregular three-dimensional surface structure or a micropore structure.
The surface of the existing metal foil is etched to form irregular surface structures or micropores by a chemical etching mode.
Wherein, the thickness of the 3D structure metal layer prepared by adopting an etching mode is 12-100 mu m.
In particular, the etching pressure during the chemical etching treatment is 2-6kg/cm2(ii) a The etching treatment temperature is 30-60 ℃; the etching solution is alkaline etching solution or acidic etching solution, preferably acidic etching solution.
Particularly, the metal foil is subjected to the chemical etching by adopting a double-sided or single-sided automatic chemical etching machine; the acid etching solution is preferably a copper chloride etching solution.
The etching method is a known conventional etching method, and other known etching methods are applicable to the present invention.
In the composite heat dissipation film, the 3D structure metal layer has the irregular three-dimensional surface structure, so that the specific surface area is increased, the heat dissipation area is increased, and the heat dissipation effect is greatly improved. In addition, the metal film layer also plays a role in electromagnetic shielding, particularly for high-frequency band electromagnetic interference, the shielding effectiveness is higher, and different thicknesses and different metal laminated layers can be designed according to different frequency band products so as to achieve corresponding shielding effectiveness.
The etched 3D structure metal layer is integrated with the heat conduction layer and the heat conduction adhesion layer into a whole through composite processing, in the composite processing process, through rolling, the irregular three-dimensional surface structure can be effectively embedded into the heat conduction layer or the heat conduction adhesion layer, namely, the peak of the 3D structure metal layer can be embedded into or pierce the heat conduction adhesion layer when the composite rolling is carried out, and an embedded combination mode is formed with the heat dissipation layer, so that the combination stability of the composite heat dissipation film is improved, the heat dissipation effect of the heat dissipation film in three dimensional directions is improved, and particularly the heat dissipation effect in the Z direction is improved.
The heat conduction layer is connected with the 3D structure metal layer in an embedded mode, the heat conduction layer can also be embedded with the heat conduction adhesive layer in an auxiliary mode, and the embedding method adopts the modes of rolling, mould pressing, compounding and the like in a pressure state.
Through the implementation processes of compounding, pressing and the like, the uneven bulges or peaks on the surface of the 3D structure metal layer are embedded into and penetrate the heat conduction adhesion layer and are contacted with heat conduction particles in the heat conduction adhesion layer to transfer heat to the heat conduction layer, and the longitudinal (namely Z-direction) penetration of the metal bulges or peaks improves the longitudinal transfer rate of the heat; the heat conducting particles of the heat conducting adhesion layer are embedded and punctured into the surface of the heat conducting layer to transfer heat to the heat conducting layer, the heat is diffused from points to surfaces, the heat dissipation is rapid, and the heat dissipation efficiency is obviously improved; and also because the heat conduction particles are embedded and punctured longitudinally (namely in the Z direction), the heat transfer rate in the longitudinal direction of the heat conduction layer (graphene layer) is improved, and the longitudinal heat dissipation efficiency of the graphene is obviously improved.
The heat conduction layer is connected with the 3D structure metal film layer in an embedded manner: the heat conducting particles are embedded into the surface of the heat conducting layer through compounding, pressing and the like in the realization process, and are embedded into the surface of the heat conducting layer through metal peaks of a 3D structure, and the embedding depth is 0.1-6 mu m.
The heat-conducting glue layer is a film layer made of heat-conducting glue, wherein the heat-conducting glue comprises glue layer resin, heat-conducting particles, a filler and a gluing diluent.
The heat conductive adhesive layer is a film layer made of a heat conductive adhesive having a heat conductive function known in the art. Any one of the heat conductive adhesives selected in the art is suitable for use in the present invention.
In particular, the heat-conducting glue also comprises conductive particles.
In particular, the heat conductive particles, the filler and the electric conductive particles in the heat conductive adhesive layer are particles with a particle size of less than 20 μm, and the particle size is preferably 5 to 20 μm, and more preferably 10 μm.
Particularly, the thickness of the heat-conducting adhesive layer is 10-30 μm.
Wherein the adhesive layer resin, the heat conducting particles and the filler in the heat conducting adhesive layer are prepared from the following components in parts by weight: 30-90 parts of adhesive layer resin, 5-50 parts of heat conducting particles and 4-20 parts of inorganic filler.
In particular, the conductive particle also comprises 5 to 20 weight parts of conductive particles.
Particularly, the adhesive layer resin is one or more of epoxy resin, acrylic resin, polyurethane resin, polyester resin or modified resin thereof, and is preferably acrylic resin or epoxy modified acrylic resin and the like; the heat conducting particles are one or more of graphene, aluminum oxide or carbon nanotubes; the inorganic filler is aluminum hydroxide or/and magnesium hydroxide, preferably aluminum hydroxide; the adhesive diluent is one or more of butanone, acetone, ethyl acetate, butyl acetate or propylene glycol monomethyl ether acetate (PMA); the conductive particles are one or more of gold, silver, nickel, copper, cadmium, chromium, zinc, iron and the like or alloy particles thereof.
And coating heat-conducting glue on the surface of the 3D structure metal layer in a coating mode, and drying to form a heat-conducting glue layer, wherein the coating mode comprises a dimple mode, a roller coating mode, a reticulate pattern mode, a spraying mode, a slit extrusion mode and the like, and preferably the slit extrusion mode and the dimple coating mode.
Conventionally used thermally conductive particles known in the art are suitable for use in the present invention. In addition to the above-described heat-conducting glues, other heat-conducting glues known in the art are suitable for use in the present invention.
Wherein the protective film layer is a PET, PEN, PI, PE or PP film.
In particular, the thickness of the protective film layer is 30 to 120 μm.
The protective film layer protects the heat-conducting adhesive layer from being polluted. When in use, the adhesive is torn off during the lamination through the protection of the processes of cutting, punching, die cutting and the like.
The invention also provides a preparation method of the composite heat dissipation film, which comprises the following steps in sequence:
1) coating heat conduction adhesive slurry on the surface of the heat conduction layer, and then drying to form a heat conduction adhesive layer to prepare a heat conduction layer-heat conduction adhesive layer composite body, wherein the surface of the heat conduction adhesive layer is uneven and has a three-dimensional irregular three-dimensional surface structure;
2) sequentially adopting a vacuum coating method and a chemical plating method to coat a film on the surface of the heat conduction adhesion layer of the heat conduction layer-heat conduction adhesion layer composite body to form a 3D structure metal layer, wherein the surface of the 3D structure metal layer is uneven and has a three-dimensional structure or irregular three-dimensional surface appearance;
3) coating heat-conducting glue on the surface of the 3D structure metal layer, and drying to form a heat-conducting glue layer;
4) and attaching a protective film layer on the surface of the heat-conducting adhesive layer to obtain the heat-conducting adhesive.
The heat conduction layer in the step 1) is a graphene sheet layer, a graphite sheet layer, or a film layer made of a heat conduction coating containing graphene or carbon nanotubes with high heat conductivity, and is preferably a graphene sheet layer.
Particularly, the thickness of the heat conducting layer is 5-300 μm, preferably 17-100 μm, and more preferably 17 μm; the thickness of the heat-conducting adhesion layer is 5-20 μm, preferably 10 μm.
The heat-conducting bonding slurry in the step 1) comprises bonding layer resin, heat-conducting particles and bonding layer diluent.
Particularly, the weight ratio of the resin of the bonding layer and the heat conducting particles in the heat conducting bonding layer is (30-90): (10-70), preferably (30-80): (15-70), and more preferably 60: 25.
Particularly, the adhesive layer resin is epoxy resin, acrylic resin, polyurethane resin, polyester resin or modified resin thereof, preferably acrylic resin; the heat conducting particles are one or more of graphene, aluminum oxide, silicon nitride or carbon nanotubes, and preferably are aluminum oxide and graphene; the adhesive layer thinner is one or more of water, butanone, acetone, ethyl acetate, butyl acetate or propylene glycol methyl ether acetate (PMA).
In particular, the thermally conductive particles have a particle size of 5 to 20 μm, preferably 10 μm. The heat conducting particles are in a particle state, and after coating and drying, an uneven three-dimensional (namely 3D) surface structure form is formed on the surface of the graphene sheet of the heat conducting layer.
Particularly, the resin of the bonding layer in the heat-conducting bonding layer is acrylic resin; the heat conducting particles are aluminum oxide and graphene.
Particularly, the weight parts of acrylic resin, alumina and graphene in the heat conduction adhesion layer are as follows: acrylic resin 60: 20, alumina: and (5) graphene.
Particularly, the weight ratio of the aluminum oxide to the graphene in the heat conducting particles is (3-5):1, and preferably 4: 1.
In particular, the coating method of the heat-conductive adhesive slurry includes knife coating, screen roller, dimple, slit, doctor blade, roller coating, screen, coating, roller pressing, spray coating, etc., and the dimple coating method is preferable.
Forming a basic metal layer with a three-dimensional structure layer or an irregular three-dimensional surface structure on the surface of the heat-conducting adhesion layer by adopting a vacuum coating method in the step 2); and forming a thickened metal layer with a three-dimensional structure layer or an irregular three-dimensional surface structure on the surface of the base metal layer by adopting a chemical plating method.
In particular, the base metal layer has a thickness of 0.05 to 0.5. mu.m, preferably 0.1 to 0.3. mu.m. The thickness of the thickened metal layer is 1-20 μm, preferably 8-20 μm.
In particular, the vacuum coating method selects vacuum evaporation plating, magnetron sputtering plating, vacuum ion plating or vacuum beam deposition, and preferably selects a magnetron sputtering plating method; the chemical plating is selected from alkaline plating or acid plating, and acid plating is preferred.
Particularly, the magnetron sputtering is realized by adopting a common power supply or a radio frequency power supply, and preferably adopts the radio frequency power supply.
In particular, the vacuum degree is controlled to be 10 in the magnetron sputtering process-1—10-5Pa, current 5-30A.
In particular, the chemical acid plating process comprises the following steps: CuSO4 70-90g/l；H2SO4180-220 g/l; HCl 40-80 ppm; 5-15ml/l of copper plating additive SCC-100-2B; the temperature is 20-24 ℃; the cathode current density is 10-40 ASF. And controlling the thickness of the plated film according to parameters such as current and the like.
The heat-conducting glue in the step 3) comprises adhesive layer resin, heat-conducting particles, a filler and an adhesive diluent.
In particular, the heat-conducting glue also comprises conductive particles.
In particular, the heat conductive particles, the filler and the electric conductive particles in the heat conductive adhesive layer are particles with a particle size of less than 20 μm, and the particle size is preferably 5 to 20 μm, and more preferably 10 μm.
Wherein the adhesive layer resin, the heat conducting particles and the filler in the heat conducting adhesive layer are prepared from the following components in parts by weight: 30-90 parts of adhesive layer resin, 5-50 parts of heat conducting particles and 4-20 parts of inorganic filler.
In particular, the conductive particle also comprises 5 to 20 weight parts of conductive particles.
Particularly, the adhesive layer resin is one or more of epoxy resin, acrylic resin, polyurethane resin, polyester resin or modified resin thereof, and is preferably acrylic resin or epoxy modified acrylic resin and the like; the heat conducting particles are one or more of graphene, aluminum oxide or carbon nanotubes; the inorganic filler is aluminum hydroxide or/and magnesium hydroxide, preferably aluminum hydroxide; the adhesive diluent is one or more of butanone, acetone, ethyl acetate, butyl acetate or propylene glycol monomethyl ether acetate (PMA); the conductive particles are one or more of gold, silver, nickel, copper, cadmium, chromium, zinc, iron and the like or alloy particles thereof.
In another aspect, the present invention provides a method for preparing a composite heat dissipation film, comprising the following steps performed in sequence:
A) carrying out chemical etching treatment on the surface of the existing metal foil to prepare a 3D structure metal layer, wherein the surface of the 3D structure metal layer is uneven and has an irregular three-dimensional surface appearance or a microporous structure;
B) coating the heat-conducting bonding slurry on the surface of the 3D structure metal layer, and then drying to form a heat-conducting bonding layer to prepare a heat-conducting bonding layer-metal layer composite;
C) placing the heat-conducting adhesion layer-metal layer complex and the graphene sheet material into a compounding machine, and adhering the adhesion layer of the heat-conducting adhesion layer-metal layer complex and the surface of the graphene sheet material heat dissipation layer together by the compounding machine to form a heat dissipation layer-adhesion layer-metal layer complex;
D) coating heat-conducting glue on the surface of the 3D structure metal layer of the heat dissipation layer-adhesion layer-metal layer composite, and drying to form a heat-conducting glue layer;
E) and attaching a protective film layer on the surface of the heat-conducting adhesive layer to obtain the heat-conducting adhesive.
Wherein, the thickness of the 3D structure metal layer prepared by adopting an etching mode in the step A) is 12-100 μm.
In particular, the etching pressure during the chemical etching treatment is 2-6kg/cm2(ii) a The etching treatment temperature is 30-60 ℃; the etching solution is alkaline etching solution or acidic etching solution, preferably acidic etching solution.
Particularly, the metal foil is subjected to the chemical etching by adopting a double-sided or single-sided automatic chemical etching machine; the acid etching solution is preferably a copper chloride etching solution.
Wherein, if both sides of the 3D structure metal layer are etched in the step B), the adhesive slurry is coated on one side; if one side of the 3D structure metal layer is etched, the side which is not etched is coated with the slurry.
The composite heat dissipation film with the 3D structure metal layer manufactured by the method is composed of a heat conduction layer, a heat conduction adhesion layer, the 3D structure metal layer, a heat conduction adhesive layer and a protection film layer which are sequentially overlapped into a whole. When the heat conducting adhesive layer is used, after cutting and punching, the protective film layer is torn down, the heat conducting adhesive layer is attached to an FPC (flexible printed circuit) or other attached objects, and the heat conducting adhesive layer can absorb and conduct heat of a workpiece and transmit the heat to the surface of the heat conducting layer through the 3D structure metal film and the heat conducting particles, so that the heat radiating effect is achieved.
Compared with the prior art, the invention has the following advantages and effects:
1. the composite heat dissipation film with the 3D structure metal film has the functions of heat dissipation and shielding, convenient processing performance and good heat dissipation and shielding effects.
2. The composite heat dissipation film of the 3D structure metal film effectively overcomes the technical problem that the existing heat dissipation film is insufficient in heat transfer and shielding functions, and effectively overcomes the defect that the graphite is insufficient in heat dissipation in the Z direction (longitudinal direction).
3. The composite heat dissipation film has a 3D structure metal layer, and has the advantages of high heat dissipation efficiency and high tensile strength compared with a conventional heat dissipation sheet.
4. The composite heat dissipation film has wide application range and is suitable for customized production.
5. The preparation method of the composite heat dissipation film is simple, simple and convenient to operate, safe and convenient, suitable for industrial popularization, light, thin, uniform and compact in film layer, soft, bendable and excellent in tensile property.
Drawings
FIG. 1 is a schematic structural diagram of a composite heat dissipation film according to the present invention;
fig. 2 is a schematic structural diagram of a 3D metal layer according to the present invention.
Description of the reference numerals
1. A heat conductive layer; 2. a heat conductive adhesive layer; 3. a 3D structure metal layer; 31. a base metal layer; 32. thickening the metal layer; 4. a heat-conducting adhesive layer; 5. a protective film layer;
Detailed Description
The invention will be further described with reference to specific embodiments, and the advantages and features of the invention will become apparent as the description proceeds. These examples are illustrative only and do not limit the scope of the present invention in any way. It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention, and that such changes and modifications may be made without departing from the spirit and scope of the invention.
Referring to fig. 1 and 2, the composite heat dissipation film of the present invention includes a heat conduction layer 1, an adhesion layer 2, a 3D structural metal layer 3, a heat conduction adhesive layer 4, and a protection film layer 5, which are closely stacked in sequence, wherein the 3D structural metal layer includes a base metal layer 31 and a thickened metal layer 32.
The other composite heat dissipation film comprises a heat conduction layer 1, a heat conduction adhesion layer 2, a 3D structure metal layer 3, a heat conduction adhesive layer 4 and a protection film layer 5 which are tightly overlapped in sequence.
The heat conducting layer is a graphene sheet layer, a graphite sheet layer, or a film layer made of a heat conducting filler containing graphene or a high heat conducting carbon nanotube material, and the thickness of the heat conducting layer is 5 to 300 μm (preferably 17 to 100 μm).
In the specific embodiment of the present invention, the heat conducting layer 1 is made of a graphene sheet with a thickness of 17 μm and a width of 140mm, except for the graphene sheet, a graphite sheet, a high heat conducting film layer formed by making a heat conducting coating from a material containing graphene or a high heat conducting carbon nanotube, or other sheets containing graphene are all suitable for the present invention, for example, a sheet containing graphene and graphite; sheets of graphene and carbon nanotubes; graphene and sheets of graphite, carbon nanotubes, and the like. The embodiments of the present invention are illustrated by graphene sheets.
The heat conduction adhesion layer 2 is a film layer, one surface of which is formed by drying and is provided with a three-dimensional surface structure or a concave-convex irregular surface structure, the surface of the heat conduction layer is coated with heat conduction adhesion slurry, and the thickness of the heat conduction adhesion layer is 5-20 mu m; the surface of the heat conduction adhesion layer is uneven and has a three-dimensional irregular and three-dimensional surface morphology structure.
The heat-conducting bonding slurry comprises bonding layer resin, heat-conducting particles and bonding layer diluent, wherein the bonding layer resin is epoxy resin, acrylic resin, polyurethane resin, polyester resin or modified resin thereof, and acrylic resin is preferred; the heat conducting particles are one or more of graphene, aluminum oxide, silicon nitride or carbon nanotubes, and preferably are aluminum oxide and graphene; the layer-by-layer diluent is one or more of water, butanone, acetone, ethyl acetate, butyl acetate or propylene glycol methyl ether acetate (PMA).
The weight ratio of the resin of the adhesive layer and the heat-conducting particles in the heat-conducting adhesive layer is (30-90): (10-70), preferably (30-80): (15-70), and more preferably 60: 25.
The heat conducting particles in the adhesion layer are in a particle state with the particle size of 5-20 microns, and after the adhesion layer is coated on the surface of the heat conducting layer and dried, the adhesion layer with the thickness of 5-20 microns is formed on the graphene sheet of the heat conducting layer, and the surface of the adhesion layer is uneven and has a three-dimensional (namely 3D) three-dimensional irregular surface structure form due to the fact that the heat conducting particles are in the particle state.
The application method of the heat-conductive adhesive slurry is a coating method such as dimple coating, knife coating, slit coating, mesh roller coating, spray coating, or a composite transfer method, and the dimple coating method is preferable.
The adhesive layer resin in the heat-conducting adhesive layer slurry is acrylic resin; the heat conducting particles are graphene and aluminum oxide, and the weight ratio of the resin of the adhesion layer to the heat conducting particles is 60:25, wherein the weight ratio of the graphene to the aluminum oxide is 20:5 (namely 4: 1).
The heat-conducting bonding slurry is formed by uniformly mixing bonding layer resin, heat-conducting particles and a proper amount of bonding layer diluent, wherein the ratio of the total weight of the bonding layer resin and the heat-conducting particles to the weight of the bonding layer diluent is (50-70): (30-50), preferably 70: 30.
In addition to the above-described formulated adhesive pastes, any adhesive paste known in the art is suitable for the thermally conductive adhesive layer of the present invention.
The heat conducting adhesive layer 2 can also be heat conducting glue or double-sided glue adhered to the surface of the heat conducting layer, and an irregular three-dimensional structure is extruded on the surface of the heat conducting glue or double-sided glue through a roller and a rolling mode to form the heat conducting adhesive layer with uneven surface and three-dimensional surface appearance. The heat conducting glue and/or the double-sided adhesive tape adopt the heat conducting glue and/or the double-sided adhesive tape materials which are known in the field.
The 3D structure metal layer 3 is a metal film layer made of gold, silver, copper, nickel, aluminum, nickel silver, nickel copper or alloy thereof, and the thickness is 1-100 μm. The metal film layer is tightly attached to the surface of the heat conduction adhesion layer, and the surface of the metal layer is uneven to form a 3D irregular surface structure.
(1) First preparation method of 3D structure metal layer
The metal layer with the 3D surface structure is prepared according to the following method: plating a metal film layer on the surface of the heat-conducting adhesion layer by adopting a vacuum coating (usually vacuum evaporation plating, magnetron sputtering plating, vacuum ion plating or vacuum beam deposition, preferably magnetron vacuum sputtering coating), namely superposing a basic metal layer on the surface of the heat-conducting adhesion layer; then, plating a metal film layer on the surface of the basic metal layer by adopting a chemical plating method (usually alkaline plating and acid plating, preferably acid plating), namely overlaying a thickened metal layer;
because the basic metal layer is a metal thin layer tightly attached to the surface of the heat-conducting adhesion layer, the surface of the adhesion layer is irregular due to the particle state of the heat-conducting particles in the adhesion layer, and the surface is in an uneven shape. And performing vacuum coating treatment on the surface of the bonding layer, copying the surface shape of the bonding layer on the surface of the formed metal film, forming a metal base film surface with a rugged structure, improving the bonding force between the film layers, and forming a base metal layer with a 3D surface structure.
The metal stack forms the thickening metal level on the basic metal level of following the surperficial structural shape of layer at the in-process metal stack that chemical plating formed the thickening metal level, forms the thickening metal level, and the unsmooth structural film surface shape of basic metal level is replicated on the thickening metal level surface that forms the thickening metal level that has 3D surface structure.
The surface of the bonding layer is uneven, and vacuum coating is realized on the surface of the bonding layer. If a thicker metal layer is required, a base metal film is vacuum-plated on the surface of the adhesion layer, and then chemical plating (such as acid plating) is performed, so that the metal layer can reach a thicker requirement, and a replicated adhesion layer structure is formed by stacking the metal layers layer by layer.
The thickness of the 3D structure metal layer prepared according to the first method is 1 to 25 μm (preferably 8 μm to 20 μm), wherein, as shown in fig. 2, the thickness of the base metal layer 31 is 0.1 to 0.5 μm (preferably 0.1 to 0.3 μm); the thickness of the thickened metal layer 32 is 1-20 μm (preferably 8-20 μm). The surface structure of the thickened metal layer is irregular and is a three-dimensional metal surface structure, namely the surface of the thickened metal layer of the 3D structure metal layer is uneven.
(2) Another preparation method of 3D structure metal layer
The metal layer with the 3D surface structure may also be prepared as follows: and carrying out chemical etching on the surface of the existing metal foil to form a film layer with an irregular three-dimensional surface structure or a microporous structure. The thickness of the 3D structure metal layer prepared according to the second method is 12-100 μm.
In the embodiment of the present invention, the metal film layer is illustrated by taking copper as an example, and other gold, silver, nickel, aluminum or alloys thereof are all suitable for the present invention. Etching the metal foil by conventional chemical etching method,
The thickness of the heat-conducting adhesive layer is 10-30 mu m, and the heat-conducting adhesive layer is formed by coating heat-conducting glue consisting of adhesive layer resin, heat-conducting particles, filler and adhesive diluent on the surface of the 3D structure metal layer and then drying.
The adhesive layer resin, the heat conducting particles and the filler in the heat conducting adhesive layer are prepared from the following components in parts by weight: 30-90 parts of adhesive layer resin, 5-50 parts of heat conducting particles, 4-20 parts of inorganic filler and 5-20 parts of conductive particles if electric conduction is needed. The heat conductive particles, the filler, and the electrically conductive particles are particles having a particle diameter of less than 20 μm (preferably 5 to 20 μm, more preferably 10 μm).
The adhesive layer resin is selected from one or more of epoxy resin, acrylic resin, polyurethane resin, polyester resin or modified resin thereof, preferably acrylic resin or epoxy modified acrylic resin and the like; the heat conducting particles are one or more of graphene, aluminum oxide or carbon nanotubes; the inorganic filler is aluminum hydroxide or/and magnesium hydroxide, preferably aluminum hydroxide; the diluent solvent is one or more of butanone, acetone, ethyl acetate, butyl acetate or propylene glycol monomethyl ether acetate (PMA); the conductive particles are one or more of gold, silver, nickel, copper, cadmium, chromium, zinc, iron and the like or alloy particles thereof.
The coating mode of the heat-conducting glue on the surface of the 3D structure metal layer is selected from a micro-concave mode, a roller coating mode, a reticulate pattern mode or a spraying mode, and the micro-concave coating mode is preferred.
In addition to the above-mentioned proportion of the heat conductive adhesive, the heat conductive adhesive known in the art is suitable for the heat conductive adhesive layer of the present invention.
The protective film layer is a PET film with the thickness of 30-120 μm. The protective film in the invention can also be a PEN, PI, PE or PP film.
Example 1
As shown in fig. 1 and 2, the composite heat dissipation film with a 3D structure metal layer of the present invention includes a heat conduction layer 1, a heat conduction adhesion layer 2, a 3D structure metal layer 3, a heat conduction adhesive layer 4, and a protection film layer 5 in sequence, wherein the 3D structure metal layer is formed by tightly laminating a base metal layer 31 and a thickened metal layer 32.
1. Preparing the heat-conducting layer
Graphene sheets with a thickness of 17 μm and a width of 140mm were selected as the thermally conductive layer.
2. Preparing a thermally conductive adhesive layer
2A) Preparing adhesive slurry
Coating heat-conducting adhesive slurry on the surface of the heat-conducting layer in a micro-concave mode, and then drying to prepare a heat-conducting adhesive layer with a three-dimensional surface structure (3D structure) with uneven surface; the thickness of the following layer is 5-20 μm, wherein the composition and weight ratio of the following slurry are (x 10 g):
adhesive layer resin 60
Thermally conductive particles 25
Then proper amount of layer diluent is added: the resin of the adhesion layer is acrylic resin; the heat conducting particles are aluminum oxide and graphene, and the ratio of the aluminum oxide to the graphene is 4: 1; the particle size of the alumina is 10 to 20 μm (usually 5 to 20 μm); the diluent of the next layer is butanone;
the heat-conducting bonding slurry is formed by uniformly mixing bonding layer resin, heat-conducting particles and a proper amount of bonding layer diluent, wherein the ratio of the total weight of the bonding layer resin and the heat-conducting particles to the weight of the bonding layer diluent is (50-70): (30-50), preferably 70: 30. The ratio of the total weight of the adhesive layer resin and the thermally conductive particles to the weight of the adhesive layer diluent in this example was 70: 30.
In the embodiment of the invention, the weight ratio of the resin of the adhesive layer to the heat-conducting particles is 60:25, and the weight ratio of the resin of the other adhesive layer to the heat-conducting particles is (30-90): (10-70), preferably (30-80): 15-70).
The resin of the adhesive layer in the embodiment of the invention is acrylic resin; the heat conducting particles are exemplified by alumina and graphene, and the ratio of alumina to graphene is 4: 1. The ratio of the aluminum oxide to the graphene can be any ratio, and is preferably (3-5): 1.
2B) coating adhesive slurry
Coating or compounding heat conduction slurry on the surface of the heat conduction layer, and drying to form a surface structure with different concave-convex appearances on the surface; the heat conducting particles are in a particle state, and after drying, an uneven three-dimensional (namely 3D) surface structure form is formed on the surface of the graphene sheet of the heat conducting layer.
The dried heat conduction adhesive layer can also be laminated into a three-dimensional structure by using a roller and a rolling mode, so that the surface appearance of the adhesive layer is a three-dimensional appearance.
The preparation of the heat-conducting adhesive layer according to the embodiment of the present invention is illustrated by taking the micro-concave manner as an example, and other coating manners such as spraying, doctor blade, slit, etc. are all applicable to the present invention.
The application method of the heat-conductive adhesive slurry is a coating method such as dimple coating, knife coating, slit coating, mesh roller coating, spray coating, or a composite transfer method, and the dimple coating method is preferable.
Selecting a coating production line with 5 sections of drying tunnels, setting the coating temperature: 70 degrees 90 degrees 110 degrees 150 degrees 80 degrees. The vehicle speed is 15 m/min.
The heat-conducting adhesive layer 2 can also be a heat-conducting adhesive tape or a double-sided adhesive tape which is attached to the surface of the heat dissipation layer, and an irregular three-dimensional structure is extruded on the surface of the heat-conducting adhesive tape or the double-sided adhesive tape in a roller and rolling mode to form the heat-conducting adhesive layer with uneven surface and three-dimensional surface appearance. The heat conducting glue and/or the double-sided adhesive tape adopt the heat conducting glue and/or the double-sided adhesive tape materials which are known in the field.
3. Preparing a 3D structure metal layer
3-1) preparing a base metal layer
Forming a metal copper film layer with a thickness of 0.20 μm (usually 0.1-0.5 μm, preferably 0.1-0.3 μm) on the surface of the heat-conducting adhesion layer by vacuum coating (vacuum plating) (vacuum magnetron sputtering method is adopted in the embodiment of the invention), namely, superposing a base metal layer 31 on the surface of the heat-conducting adhesion layer; wherein: the control conditions of magnetron sputtering are as follows: degree of vacuum 10-1—10-5Pa, current 5-30A. The basic metal layer is a metal layer thickening foundation, and the surface structure of the bonding layer is copied at the same time, so that the metal layer has an irregular three-dimensional surface structure, and the basic metal layer has the same 3D structure appearance as the heat conduction bonding layer.
The preparation of the basic metal layer in the embodiment of the invention is illustrated by taking magnetron sputtering as an example, except for magnetron sputtering, other vacuum coating modes, such as vacuum evaporation plating, vacuum sputtering plating, vacuum ion plating, vacuum plasma plating or vacuum beam deposition, are all applicable to the invention; besides copper, other metals such as gold, silver, nickel, aluminum, nickel silver, nickel copper or alloys thereof are suitable for the present invention, and copper is exemplified in the embodiments of the present invention.
3-2) overlapping the thickened metal layer
A metal copper film layer with a thickness of 10 μm (usually 1-20 μm, preferably 8-20 μm) is plated on the surface of the base metal layer by using an acid electroplating method, i.e. the thickened metal layer 32 is stacked, wherein the process conditions of the acid electroplating are as follows: CuSO4 70-90g/l；H2SO4180-220 g/l; HCl 40-80 ppm; 5-15ml/l of copper plating additive SCC-100-2B; the temperature is 20-24 ℃; the cathode current density is 10-40 ASF; the deposition rate is 0.45-1 um/min. The surface appearance of basic metal level is duplicated to the thickening metal level, thickening metal level one deck three-dimensional metal surface structure or the rete of irregular three-dimensional surface structure of basic metal level's surface deposit, and the thickening metal level has the 3D structural morphology the same with basic metal level, heat conduction adhesion layer, and surface irregularity, basic metal level and thickening metal level form the 3D structure metal level on graphite alkene heat conduction layer surface.
4. Superposed heat-conducting adhesive layer
4A) Preparing heat-conducting glue
Coating heat-conducting glue on the uneven surface with the three-dimensional structure of the 3D structure metal layer in a slit extrusion mode, and then drying the heat-conducting glue until the surface is dry to form a heat-conducting glue layer; wherein the heat-conducting glue comprises the following components in parts by weight (multiplied by 10 g):
wherein, the adhesive layer resin is acrylic resin; the heat conducting particles are graphene particles; the inorganic filler is aluminum hydroxide particles; the adhesive diluent is ethyl acetate; the solid substances (heat conductive particles, inorganic filler) in the coating are all in powder form, and the average particle size is 20 μm (preferably 10 μm).
The adhesive layer resin in the embodiment of the present invention is illustrated by taking an acrylic resin as an example, and besides the acrylic resin, other polyurethane resin, epoxy resin, polyimide resin, or modified resin thereof is suitable for the present invention; the heat conducting particles are illustrated by taking graphene particles as an example, and besides the graphene particles, other aluminum oxide and carbon nanotubes are suitable for the invention; the inorganic filler is exemplified by aluminum hydroxide particles, and may be magnesium hydroxide or the like in addition to aluminum hydroxide particles; the adhesive diluent is exemplified by ethyl acetate, and other volatile organic solvents such as methyl ethyl ketone, acetone, butyl acetate, propylene glycol methyl ether acetate (PMA), and the like are suitable for use in the present invention.
4B) Coating heat-conducting glue
The raw materials are uniformly mixed according to the proportion to prepare the heat-conducting glue, and then the heat-conducting glue is coated on the surface of the 3D structure metal layer.
The thickness of the heat-conducting adhesive layer is 10 μm (usually 10-30 μm), the drying temperature is 150 + -10 deg.C, the drying time to surface is 50 + -5 s, the drying tunnel length is 24 m, and the coating speed is 10-20 m/min.
In addition to the above-mentioned proportion of the thermally conductive adhesive, the thermally conductive adhesive known in the art is suitable for the present invention.
The application method of the heat-conducting glue in the embodiment of the present invention is exemplified by slit extrusion, and other application methods such as mesh roll, reticulate pattern, scraper, dimple, etc. are applicable to the present invention except for slit extrusion.
5. Laminating protective film layer
A PET polyester film with the thickness of 50 micrometers (usually 23-120 micrometers) is attached to the surface of the prepared heat-conducting adhesive layer by adopting an on-line and off-line composite process method to serve as a protective film layer.
The protective film is a known release film having a release function. The protective film can be made of PET, PEN, PI, PE or PP film.
When in use, after cutting and punching, the protective film layer is torn off, and the bonding layer is bonded on FPC (flexible printed circuit) or other stuck objects, for example, when the bonding layer is acrylic glue, the bonding layer can be bonded at normal temperature. Fit parameters known in the art are all suitable for the present invention.
The shielding effectiveness of the composite heat-dissipating film having a 3D-structured metal layer prepared according to the method of the present invention was tested according to standard SJ20524-1995 "test method for shielding effectiveness of materials", and the test results are shown in table 1.
Table 1 shows the shielding effect of the composite heat-dissipating film
| Film thickness | Frequency range | Shielding effectiveness | |
| Example 1 | 35μm | 3000MHz | 80.5dB |
| Example 1A | 35μm | 3000MHz | 80.5dB |
| Example 2 | 50μm | 3000MHz | 80.5dB |
| Comparative example 1 | 17μm | 3000MHz | 26.0dB |
| Comparative example 2 | 50μm | 3000MHz | 80.5dB |
The heat dissipation performance of the composite heat dissipation film with the 3D structure metal layer prepared by the method is tested, and the test result is shown in table 2.
The experimental method for testing the heat dissipation performance of the composite heat dissipation film comprises the following steps: testing at 25 ℃ in a constant temperature chamber, selecting a heat source (the test selects a COF flexible circuit board and one side IC to connect a display screen for testing, BOE makes T255), attaching a heat dissipation film and a comparison sample on the other side of a workpiece (COF), testing 9 point positions with equal distance at the position where the workpiece is attached to the heat dissipation film by using an infrared temperature tester after the temperature of the heat dissipation film and the comparison sample is stable (the test selects 10 minutes), and taking an average value.
Table 2 test results of heat dissipation effect of the composite heat dissipation film
Example 1A
The same as example 1 was repeated except that the thermally conductive glue in step 4) further contained electrically conductive particles in an amount of 15 parts by weight, the electrically conductive particles were copper powder, and the average particle size of the copper powder was 10 μm.
In the embodiment of the present invention, copper powder is used as an example of the conductive particles, and nickel, copper, and silver (powder) are all suitable for the present invention.
The heat dissipation and shielding effects of the prepared composite heat dissipation film are shown in tables 1 and 2.
Example 2
As shown in fig. 1, the heat dissipation shielding film with a 3D structure metal layer of the present invention sequentially includes a heat conduction layer 1, a heat conduction adhesion layer 3, a 3D structure metal layer 2, a heat conduction adhesive layer 3, and a protection film layer 4 from top to bottom.
1. Preparing the heat-conducting layer
Same as in step 1) of example 1.
2. Preparing a 3D structure metal layer
The manufacturing method of the 3D structure metal layer can be prepared according to the following method: and carrying out chemical etching on the surface of the existing metal foil to form a film layer with an irregular three-dimensional surface structure or a microporous structure.
Etching a copper foil having a thickness of 18 μm (usually 12 to 100 μm) by using a double-sided automatic type chemical etching machine under an etching pressure of 2 to 6kg/cm2(ii) a The etching treatment temperature is 30-60 ℃; the etching solution is copper chloride etching solution, and a 3D structure metal layer with uneven surface and irregular three-dimensional surface appearance with the thickness of 18 mu m is prepared.
In addition to acid etching, alkaline etching is also suitable for use in the etching process of the present invention; besides copper chloride etching solution, other alkaline copper chloride, iron sulfide, ammonium persulfate and the like are also suitable for the invention. The 3D structure metal layer can be etched on a single side or double sides.
In addition to the above-described etching methods, etching methods known in the art are applicable to the present invention. The etching method is a known conventional etching method, and the 3D structure metal layer prepared by the method has the thickness of 12-100 mu m.
In the embodiment of the present invention, the metal film layer is illustrated by taking copper as an example, and other gold, silver, nickel, aluminum or alloys thereof are all suitable for the present invention.
3. Preparing a thermally conductive adhesive layer
3A) Preparing adhesive slurry
Same as step 2A) of example 1;
3B) coating adhesive slurry
Coating the prepared bonding slurry on the surface of the 3D structure metal layer prepared by adopting a chemical etching method in the step 2), and drying to form a heat conduction bonding layer-metal layer composite;
if the 3D structure metal layer is etched in a single side, the paste is coated on the metal layer which is not etched.
4. Preparing a heat dissipation layer-adhesive layer-3D structure metal layer composite
And placing the heat-conducting adhesion layer-metal layer composite and the graphene sheet heat-radiating layer in a compounding machine, and adhering the adhesion layer of the heat-conducting adhesion layer-metal layer composite and the surface of the graphene sheet heat-radiating layer together by the compounding machine to form the heat-radiating layer-adhesion layer-metal layer composite.
5. Superposed heat-conducting adhesive layer
Same as in step 4) of example 1.
6. Laminating protective film layer
Same as in step 5) of example 1.
The heat dissipation and shielding effects of the prepared composite heat dissipation film are shown in tables 1 and 2.
Comparative example 1
The heat dissipation film formed by directly superimposing the protective film layer on the graphene sheet heat conduction layer was used as comparative example 1, and the heat dissipation and shielding effects of the prepared heat dissipation film are shown in tables 1 and 2.
Comparative example 2
The copper foil is not etched except in the step 2); step 3) the same as in example 2 was repeated except that the following slurry was directly coated on the surface of the copper foil.
The heat dissipation and shielding effects of the prepared heat dissipation film are shown in tables 1 and 2. Although the shielding effectiveness is the same, the heat dissipation effect is obviously different.
The above-described embodiments of the present invention are merely exemplary and do not limit the scope of the present invention in any way. It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention, and that such changes and modifications may be made without departing from the spirit and scope of the invention.
Claims (10)
1. A composite heat dissipation film is characterized by comprising a heat conduction layer, a heat conduction adhesion layer, a 3D structure metal layer, a heat conduction adhesive layer and a protection film layer which are tightly overlapped in sequence.
2. The composite heat spreading film of claim 1, wherein the thermally conductive layer is a graphene sheet layer, a graphite sheet layer, or a film layer made of a thermally conductive coating containing graphene or carbon nanotubes.
3. The composite heat dissipation film of claim 1 or 2, wherein the metal of the 3D structure metal layer is selected from one or an alloy of any two metals of gold, silver, copper, nickel and aluminum.
4. The composite heat dissipating film according to claim 1 or 2, wherein the surface of the thermally conductive adhesive layer is uneven; has three-dimensional irregular surface topography; the surface of the 3D structure metal layer is uneven; has three-dimensional irregular surface topography.
5. The composite heat dissipating film of claim 1 or 2, wherein the protective film layer is a PET, PEN, PI, PE, or PP film.
6. The composite heat dissipation film of claim 1 or 2, wherein the thickness of the thermal conductive adhesive layer is 10 to 30 μm; the thickness of the protective film layer is 23-120 mu m.
7. The preparation method of the composite heat dissipation film is characterized by comprising the following steps of:
1) coating heat conduction adhesive slurry on the surface of the heat conduction layer, and then drying to form a heat conduction adhesive layer to prepare a heat conduction layer-heat conduction adhesive layer composite body, wherein the surface of the heat conduction adhesive layer is uneven and has a three-dimensional irregular three-dimensional surface structure;
2) sequentially adopting a vacuum coating method and a chemical plating method to coat a film on the surface of the heat conduction adhesion layer of the heat conduction layer-heat conduction adhesion layer composite body to form a 3D structure metal layer, wherein the surface of the 3D structure metal layer is uneven and has a three-dimensional structure or irregular three-dimensional surface appearance;
3) coating heat-conducting glue on the surface of the 3D structure metal layer, and drying to form a heat-conducting glue layer;
4) and attaching a protective film layer on the surface of the heat-conducting adhesive layer to obtain the heat-conducting adhesive.
8. The method of claim 7, wherein in step 1) the thermally conductive layer is a graphene sheet layer, a graphite sheet layer, or a film layer made of a thermally conductive coating containing graphene or highly thermally conductive carbon nanotubes, preferably a graphene sheet layer.
9. The preparation method of the composite heat dissipation film is characterized by comprising the following steps of:
A) carrying out chemical etching treatment on the surface of the existing metal foil to prepare a 3D structure metal layer, wherein the surface of the 3D structure metal layer is uneven and has an irregular three-dimensional surface appearance or a microporous structure;
B) coating the heat-conducting bonding slurry on the surface of the 3D structure metal layer, and then drying to form a heat-conducting bonding layer to prepare a heat-conducting bonding layer-metal layer composite;
C) placing the heat-conducting adhesion layer-metal layer complex and the graphene sheet material into a compounding machine, and adhering the adhesion layer of the heat-conducting adhesion layer-metal layer complex and the surface of the graphene sheet material heat dissipation layer together by the compounding machine to form a heat dissipation layer-adhesion layer-metal layer complex;
D) coating heat-conducting glue on the surface of the 3D structure metal layer of the heat dissipation layer-adhesion layer-metal layer composite, and drying to form a heat-conducting glue layer;
E) and attaching a protective film layer on the surface of the heat-conducting adhesive layer to obtain the heat-conducting adhesive.
10. The method according to claim 9, wherein in step B), if both sides of the 3D structure metal layer are etched, the adhesive slurry is selectively applied to one side; if one side of the 3D structure metal layer is etched, the side which is not etched is coated with the slurry.
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| CN114801357A (en) * | 2022-04-28 | 2022-07-29 | 安徽碳华新材料科技有限公司 | Heat radiation structure for integrated chip based on film-like artificial graphite sheet |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114801357A (en) * | 2022-04-28 | 2022-07-29 | 安徽碳华新材料科技有限公司 | Heat radiation structure for integrated chip based on film-like artificial graphite sheet |
| CN114801357B (en) * | 2022-04-28 | 2024-02-09 | 安徽碳华新材料科技有限公司 | Heat radiation structure for integrated chip based on film-shaped artificial graphite sheet |
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