CN106671501A - Highly heat-resistant graphite film metal composite and preparation method thereof - Google Patents

Highly heat-resistant graphite film metal composite and preparation method thereof Download PDF

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Publication number
CN106671501A
CN106671501A CN201710024795.3A CN201710024795A CN106671501A CN 106671501 A CN106671501 A CN 106671501A CN 201710024795 A CN201710024795 A CN 201710024795A CN 106671501 A CN106671501 A CN 106671501A
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China
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fire resistance
thermoplastic resin
graphite film
resin adhesives
solvent
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CN201710024795.3A
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Chinese (zh)
Inventor
刘佩珍
李鑫
蔡航行
戴曛晔
吕新坤
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重庆云天化瀚恩新材料开发有限公司
云南云天化股份有限公司
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Priority to CN201710024795.3A priority Critical patent/CN106671501A/en
Publication of CN106671501A publication Critical patent/CN106671501A/en

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    • 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
    • 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
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • 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
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/06—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
    • 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
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
    • 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
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
    • B32B37/1284—Application of adhesive
    • 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
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/0012—Mechanical treatment, e.g. roughening, deforming, stretching
    • 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
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/16—Drying; Softening; Cleaning
    • B32B38/164—Drying
    • 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
    • B32B9/00—Layered products comprising a particular substance not covered by groups B32B11/00 - B32B29/00
    • B32B9/005—Layered products comprising a particular substance not covered by groups B32B11/00 - B32B29/00 comprising one layer of ceramic material, e.g. porcelain, ceramic tile
    • B32B9/007—Layered products comprising a particular substance not covered by groups B32B11/00 - B32B29/00 comprising one layer of ceramic material, e.g. porcelain, ceramic tile comprising carbon, e.g. graphite, composite carbon
    • 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
    • B32B9/00—Layered products comprising a particular substance not covered by groups B32B11/00 - B32B29/00
    • B32B9/04—Layered products comprising a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B9/041—Layered products comprising a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material of metal
    • 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
    • C08K3/04—Carbon
    • 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
    • C08K3/28—Nitrogen-containing compounds
    • 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
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/22—Expanded, porous or hollow particles
    • C08K7/24—Expanded, porous or hollow particles inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIAL AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIAL AS ADHESIVES
    • C09J179/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09J161/00 - C09J177/00
    • C09J179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C09J179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • 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
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/16—Drying; Softening; Cleaning
    • B32B38/164—Drying
    • B32B2038/168—Removing solvent
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
    • B32B2307/212—Electromagnetic interference shielding
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/306—Resistant to heat
    • 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
    • B32B2457/00—Electrical equipment
    • 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
    • C08K3/28—Nitrogen-containing compounds
    • C08K2003/282—Binary compounds of nitrogen with aluminium

Abstract

The invention discloses a highly heat-resistant graphite film metal composite and a preparation method thereof. The highly heat-resistant graphite film metal composite comprises a graphite film layer, a surface-roughened metal layer and a highly heat-resistant thermoplastic resin layer. A single-layer or multi-layer highly heat-resistant graphite film metal composite is obtained by preparing a highly heat-resistant thermoplastic resin adhesive, treating the surface of the metal layer, preparing the composite and other steps. The preparation method provided by the invention is simple and the prepared highly heat-resistant graphite film metal composite has excellent thermal conductivity and excellent heat resistance and solvent resistance, can be electromagnetically shielded, and is suitable for use in electronic and electric equipment with high heat dissipation and high heat resistance requirements.

Description

A kind of high-fire resistance graphite film metallic composite and preparation method thereof

Technical field

The present invention relates to a kind of high-fire resistance graphite film metallic composite and preparation method thereof, the high-fire resistance graphite Metal composite film is applied to electronics, the electrical equipment for having high-termal conductivity and high-fire resistance demand.

Background technology

With electronics, the expansion of electrical equipment range of application and popularization, wanting to electronics, the performance of electrical equipment and structure Ask increasingly harsher with complicated, such as higher processing speed, less volume, lighter weight, higher power and more preferably Heat dispersion etc., especially as the continuous expansion of new-energy automobile market scale in recent years, to automobile fast charging and discharging equipment Demand be continuously increased, the heat conductivity and heat dispersion of material are put forward higher requirement.

Because the microprocessor and integrated circuit in electronics, electrical equipment and system or in high power optical devices all can Very high heat is produced, but microprocessor, integrated circuit and other electronic devices and components are typically only capable in limited temperature model Interior effectively normal operation is enclosed, if the heat that these electronic devices and components are produced exceedes the scope for allowing, not only to their own Performance is impacted, it is also possible to performance to whole system and stably cause immeasurable infringement.It is well known that electronics, electricity The temperature of the performance, reliability and life-span and running environment of gas equipment inversely, by taking automobile fast charging and discharging equipment as an example： The charging pile of power 60KW and communication power cabinet are compared, only module heat dissipating amount just reaches 60*0.05*1000=3000W（Mesh Forward owner's flow module efficiency nominal 95%）, it means that in charging process, the heat of generation is equal volume bar to charging pile 3 times of the outdoor cabinet heat dissipation capacity that communicates under part, and charging rate is faster, charging pile inductor module power is bigger, and charging current is got over Greatly, i.e., the heat that the element such as inductor module, power module is produced is bigger, and this heat dissipation equipment to charging pile proposes tightened up Require.As the requirement of the discharge and recharge to charging pile, charge/discharge rates is improved constantly, and electronic devices and components are miniaturized, Light-weighted to require constantly to improve, the requirement to radiating control and heat dissipation design is increasingly strict.

Traditional heat sinks during especially as single use, can not meet current industrial and section with significantly restricted The demand of skill Great War.In recent years, heat-conductive composite material is with its low cost, easy processing, good electrical insulating property and mechanical property etc. Advantage is received significant attention, and its preparation method also becomes the focus of current research, the main application model of current heat-conductive composite material Enclose including fields such as microelectronics, electric electrician, space flight and aviation.

A kind of native graphite/copper heat sink compound of application number CN201510672288 patent disclosures and preparation method thereof, It is that pretreatment is carried out to copper foil surface, removes pollution and the oxide layer of copper foil surface, then be roughened and cured, makes Copper Foil Surface forms the roughened layer for being evenly distributed with warty copper grain structure；Again bulk electrographite monolithic is rolled over into fractal film On, artificial plumbago single slice is attached on fractal film；Finally by the one side of fractal film derived above with electrographite monolithic It is laid on the Copper Foil of Jing process, the stage calenderings of Jing obtain electrographite/copper heat sink compound, the implementing process is complicated. Application number CN201210169318 patents provide a kind of new high heat conduction heat radiation coating and its manufacture method, including base resin And filler, wherein base resin is coating resin, and filler is by graphite, nano-graphite, Graphene, CNT, carbon fiber, gold One or more composition of category fiber, zirconium oxide, boron nitride and copper, aluminum metal powder body etc., the coating can directly be coated or sprayed The surface of radiator is coated in, in use heat is transmitted on coating, coating is dispersed into heat in space again, accelerates to dissipate Send out the heat that electronic devices and components are produced.Publication No. CN203110435U patent describes a kind of graphite Copper Foil compound film sheet, should Compound film sheet mainly includes Copper Foil, graphite substrate layer and PET mould release membrances, and arrangement, and Copper Foil and graphite are stacked gradually from top to down Have the first conductive layer between base material, graphite substrate it is release with PET it is intermembranous have the second conductive layer, so as to realize lightweight, the conduction of product And radiating effect is good, but conducting resinl is relatively costly, is unfavorable for cost declining.Publication number CN105086659A patents describe one The preparation method of kind of high heat conducting nano carbon Copper Foil, i.e., by it is a kind of be mixed with nanometer radiate slurry adhesive preparation, and by its Directly coat with Copper Foil, heated drying and processing obtains a kind of nano-sized carbon Copper Foil of high heat conduction, the resin used by the patent For Kynoar or epoxy resin or polyurethane or polyacrylate.

Above-mentioned patent is not used resistant to elevated temperatures matrix resin adhesive.It is known that polyurethane, polyacrylic acid The solvent resistance of the matrix resins such as resin is poor and thermostability is relatively low, and conventional conducting resinl the making because of expensive metal powder in market With cost is of a relatively high, and this graphite film Copper Foil composite for allowing for being obtained by usual resins or conducting resinl cannot be tackled Increasingly harsher use environment is required and cost degradation.

The content of the invention

For problem above, it is an object of the invention to provide a kind of graphite film gold with high-fire resistance, resistance to Conventional solvents Category composite and preparation method thereof.Preparation method is simple of the present invention, the high heat resistant type graphite film metallic composite tool of preparation There are excellent heat conductivility and excellent thermostability and solvent resistance, can be electromagnetically shielded, it is adaptable to have high radiating, high-fire resistance In electronics, the electrical equipment of demand.

The present invention provide technical scheme be：

A kind of high-fire resistance graphite film metallic composite, the high-fire resistance graphite film metallic composite is included from top to bottom Graphite film layer, high-fire resistance thermoplastic resin layer and the metal level through surface coarsening process.

The high-fire resistance thermoplastic resin layer is made up of high-fire resistance thermoplastic resin adhesives, the high-fire resistance heat Plastic resin adhesive includes thermoplastic resin adhesives, heat filling and solvent.

The thickness specification of the graphite film is the different sizes such as 12um, 17um, 25um or 40um.

The metal level is metal forming, preferably Copper Foil or tinfoil paper；The thickness specification of the metal forming be 12um, 18um or The different sizes such as 35um.

The high-fire resistance thermoplastic resin layer is dissolved in solvent by thermoplastic resin adhesives, is stirred under room temperature to complete Dissolving, adds heat filling to stir under certain condition and prepares.

The thermoplastic resin adhesives are TPI class adhesive；The TPI class gluing Agent is dissolved in high boiling organic solvent by modified TPI powder and is obtained；The high boiling organic solvent is DMAC or DMF.

In the high-fire resistance thermoplastic resin adhesives, in parts by weight, thermoplastic polyimide resin accounting is 10- 35%；Heat filling accounting is 0.5-14.5%；The solvent accounting is 51-89%.

Preferably, in the high-fire resistance thermoplastic resin adhesives, in parts by weight, thermoplastic polyimide resin is accounted for Than for 15-30%；Heat filling accounting is 0.5-10%；The solvent accounting is 65-80%.

Present invention also offers a kind of preparation method of high-fire resistance graphite film metallic composite, methods described include with Lower step：

Step 1）Prepare high-fire resistance thermoplastic resin adhesives：Thermoplastic resin adhesives are dissolved in solvent, are stirred under room temperature Mix to being completely dissolved, add heat filling to stir at a certain temperature, obtain high-fire resistance thermoplastic resin adhesives；Step 2） Process layer on surface of metal：The side surface of metal level one is carried out into roughening treatment, formed increase surface adhesion force with concavo-convex anchoring The metal level through surface coarsening process of structure；Step 3）Prepare composite：By the high-fire resistance thermoplastic resin for obtaining Adhesive coating device coats the unilateral roughening face of the metal level through surface coarsening process, after drying process, then Its opposite side coating high-fire resistance thermoplastic resin adhesives is formed into sticky surface under uniform temperature, solvent and and graphite film is removed Pressing, obtains the high-fire resistance graphite film metallic composite of monolayer.

Present invention also offers the preparation method of another kind of high-fire resistance graphite film metallic composite, methods described includes Following steps：

Step 1）Prepare high-fire resistance thermoplastic resin adhesives：Thermoplastic resin adhesives are dissolved in solvent, are stirred under room temperature Mix to being completely dissolved, add heat filling to stir at a certain temperature, obtain high-fire resistance thermoplastic resin adhesives；Step 2） Process layer on surface of metal：The both side surface of metal level carries out roughening treatment, formed increase surface adhesion force with concavo-convex The metal level through surface coarsening process of anchor structure；Step 3）Prepare composite：By the high-fire resistance thermoplasticity for obtaining Resin adhesive coating device coats the roughening face of the upper and lower surface of the metal level through surface coarsening process, at drying After reason, then at a certain temperature by both sides be coated with high-fire resistance thermoplastic resin adhesives formed sticky surface, remove solvent simultaneously With graphite film pressing, the high-fire resistance graphite film metallic composite of bilayer is obtained.According to this, the different numbers of plies can as needed be obtained High-fire resistance graphite film Copper Foil composite.

Further, step 1）In, the thermoplastic resin adhesives are TPI class adhesive；The heat Plastic polyimide class adhesive is dissolved in high boiling organic solvent by modified TPI powder and is obtained；It is described High boiling organic solvent is DMAC or DMF.

Further, step 1）In, in the high-fire resistance thermoplastic resin adhesives, in parts by weight, thermoplastic poly Imide resin accounting is 10-35%；Heat filling accounting is 0.5-14.5%；The solvent accounting is 51-89%.

Preferably, in the high-fire resistance thermoplastic resin adhesives, in parts by weight, thermoplastic polyimide resin is accounted for Than for 15-30%；Heat filling accounting is 0.5-10%；The solvent accounting is 65-80%.

Further, step 1）In, the heat filling is ultra-fine electrographite powder, Nano graphite powder, CNT, nitrogen Change the one or more of which of the heat fillings such as boron, aluminium nitride；The ultra-fine electrographite powder is by generation in graphite film production Waste material Jing is broken, grinding etc. is processed and is obtained, and is conducive to the recovery of waste material and the reduction of cost.

Further, step 2）In, the metal in the metal level is metal forming, preferably Copper Foil or tinfoil paper；The gold The thickness specification of category paper tinsel is the different sizes such as 12um, 18um or 35um.

Further, step 3）In, the thickness specification of the graphite film is the different rule such as 12um, 17um, 25um or 40um Lattice.

Further, step 3）In, the surface layer that the coating high-fire resistance thermoplastic resin adhesives form sticky surface is thick Spend for 2um to 10um；The temperature for removing solvent is 140 DEG C -170 DEG C, and the time for removing solvent is 2min-7min； The temperature of the pressing is 120 DEG C -190 DEG C；The coating device is automatic film applicator.

The present invention compared with prior art, has the advantage that and has the beneficial effect that：

(1) high-fire resistance of the present invention, the graphite film metallic composite low cost of resistance to Conventional solvents, preparation method letter It is single, can be obtained with conventional coating-heat treatment mode.

(2) high-fire resistance, the graphite film metallic composite of resistance to Conventional solvents that prepared by the present invention not only has excellent Heat conductivility, also with fabulous resistance to Conventional solvents and high-temperature stability, the heat-resisting quantity and solvent resistance of material are significantly carried Rise, not stratified under multi-solvents environment, within 500 DEG C environment is hardly weightless, overcome in current material heat under low temperature The shortcomings of losing big, poor solvent resistance again.

(3) high-fire resistance, the graphite film metallic composite of resistance to Conventional solvents that prepared by the present invention has good simultaneously Electromagnetic shielding characteristic, applicable use environment extensively, is used it for preparing the electronic devices and components in high-end electronic, electrical equipment Afterwards, the thermostability of electronic devices and components, reliability and service life will be greatly promoted.

Description of the drawings

Fig. 1 is the structural representation of the high-fire resistance graphite film metallic composite of the present invention；

Label in figure：1- graphite film layers；2- high-fire resistance thermoplastic resin layers；The metal level that 3- is processed through surface coarsening；

Fig. 2 is the structural representation of another kind of high-fire resistance graphite film metallic composite of the present invention；

Label in figure：1- graphite film layers；2- high-fire resistance thermoplastic resin layers；The metal level that 3- is processed through surface coarsening；4- Second high-fire resistance thermoplastic resin layer；5- the second graphite film layers.

Specific embodiment

In order to deepen the understanding of the present invention, below in conjunction with original of the drawings and specific embodiments to composite of the present invention Reason, preparation process are described in further detail：

Embodiment 1

15 parts of self-control TPI powder are made an addition in 80 parts of DMF solvent, is stirred at room temperature to being completely dissolved； The ultra-fine electrographite powder that 5 parts of Jing are processed is added thereto again, at 40 DEG C 2h is stirred, obtain TPI adhesive； The TPI adhesive automatic film applicator for obtaining is coated into the roughening face of Copper Foil, the drying and processing at 140 DEG C 5min, then press its sticky surface and graphite film at 160 DEG C, graphite film Copper Foil composite is obtained, it is designated as embodiment 1.

Embodiment 2

25 parts of self-control TPI powder are made an addition in 70 parts of DMF solvent, is stirred at room temperature to being completely dissolved； 4.5 parts of Jing are processed ultra-fine electrographite powder and 0.5 part of aluminium nitride again is added thereto, and at 50 DEG C 2h is stirred, and obtains heat Plastic polyimide adhesive；The TPI adhesive automatic film applicator for obtaining is coated into the roughening of Copper Foil Face, the drying and processing 5min at 140 DEG C, then press its sticky surface and graphite film at 160 DEG C, obtain graphite film Copper Foil and be combined Material, is designated as embodiment 2.

Embodiment 3

20 parts of self-control TPI powder are made an addition in 75 parts of DMF solvent, is stirred at room temperature to being completely dissolved； 3 parts of Jing are processed ultra-fine electrographite powder, 1 part of CNT and 1 part of aluminium nitride again is added thereto, and stirs at 30 DEG C 3h, obtains TPI adhesive；The TPI adhesive automatic film applicator for obtaining is coated into Copper Foil Roughening face, the drying and processing 4min at 150 DEG C, then press its sticky surface and graphite film at 170 DEG C obtains graphite film copper Paper tinsel composite, is designated as embodiment 3.

Embodiment 4

28 parts of self-control TPI powder are made an addition in 65 parts of DMAc solvents, is stirred at room temperature to completely molten Solution；2 parts of Jing are processed ultra-fine electrographite powder, 4 parts of CNT and 2 parts of aluminium nitride again is added thereto, and stirs under room temperature 4h is mixed, TPI adhesive is obtained；The TPI adhesive automatic film applicator for obtaining is coated into copper The roughening face of paper tinsel, the drying and processing 5min at 160 DEG C, then press its sticky surface and graphite film at 180 DEG C, obtain graphite film Copper Foil composite, is designated as embodiment 4.

Embodiment 5

25 parts of self-control TPI powder are made an addition in 73 parts of DMAc solvents, is stirred at room temperature to completely molten Solution；The ultra-fine electrographite powder that 2 parts of Jing are processed is added thereto again, at 45 DEG C 4h is stirred, obtain TPI gluing Agent；The TPI adhesive automatic film applicator for obtaining is coated into the roughening face of Copper Foil, at drying at 160 DEG C Reason 4min, then press its sticky surface and graphite film at 180 DEG C, graphite film Copper Foil composite is obtained, it is designated as embodiment 5.

Comparative example

Commercial polypropylene acid esters adhesive automatic film applicator is coated into the roughening face of Copper Foil, the drying and processing at 90 DEG C 5min, then press its sticky surface and graphite film at 80 DEG C, obtain graphite film Copper Foil composite comparative example.

The graphite film Copper Foil composite sample that above example 1 to embodiment 5 and comparative example is obtained cuts into The print of 90*120mm specifications, carries out infrared conduction of heat test, and test result refers to table 1.

The infrared conduction of heat test result of the graphite film Copper Foil composite of table 1

The graphite film Copper Foil composite print that embodiment 1 to embodiment 5 and comparative example is obtained, is separately immersed in fourth 30min in ketone, acetone, ethyl acetate, alcohol solvent, the solvent resistance of test sample；Meanwhile, by TPI powder TGA tests, test condition are carried out respectively with except the polyacrylate adhesives after solvent：Under nitrogen atmosphere, 10 DEG C of heating rate/ Min, is warming up to 800 DEG C.Test result is shown in Table 2.

The solvent resistance test of the graphite film Copper Foil composite of table 2 and the thermal weight loss test result of adhesive

Note：The TPI adhesive being not restricted under the weightless temperature.

Knowable to the test result of Tables 1 and 2, a kind of graphite based on high-fire resistance thermoplastic resin described herein Film metallic composite has excellent heat conductivility and excellent thermostability and solvent resistance, can be electromagnetically shielded, it is adaptable to have In high radiating, the electronics of high-fire resistance demand, electrical equipment.

The present invention and its specific embodiment are described above, finally it should be noted that：Above-mentioned embodiment or reality Apply the exhaustion of example not specific embodiment, above-described embodiment is intended to indicate that the present invention, and the protection of the unrestricted present invention Scope, for the ordinary skill in the art, without departing from the principles and spirit of the present invention, can be to this A little specific embodiments or embodiment carry out various changes, modification, replacement and modification, and these are designed without performing creative labour Go out and the same or analogous structure of the technical program, device, equipment or product and its using method and/or purposes, all should cover Within protection scope of the present invention.

Claims (10)

1. a kind of high-fire resistance graphite film metallic composite, it is characterised in that：The high-fire resistance graphite film Metals composite Material includes from top to bottom graphite film layer, high-fire resistance thermoplastic resin layer and the metal level through surface coarsening process；The height Heat resistant thermoplastic's resin bed is made up of high-fire resistance thermoplastic resin adhesives, the high-fire resistance thermoplastic resin adhesives Comprising thermoplastic resin adhesives, heat filling and solvent；In parts by weight, the thermoplastic resin adhesives accounting is 10- 35%；Heat filling accounting is 0.5-14.5%；The solvent accounting is 51-89%.
2. high-fire resistance graphite film metallic composite according to claim 1, it is characterised in that：The thickness of the graphite film Metric lattice are 12um, 17um, 25um or 40um.
3. high-fire resistance graphite film metallic composite according to claim 1, it is characterised in that：The metal level is gold Category paper tinsel；The thickness specification of the metal forming is 12um, 18um or 35um.
4. a kind of preparation method of the high-fire resistance graphite film metallic composite as described in any one of claim 1-3, it is special Levy and be：Described method is comprised the following steps；
Step 1）Prepare high-fire resistance thermoplastic resin adhesives：Thermoplastic resin adhesives are dissolved in solvent, are stirred under room temperature Mix to being completely dissolved, add heat filling to stir at a certain temperature, obtain high-fire resistance thermoplastic resin adhesives；
Step 2）Process layer on surface of metal：The side surface of metal level one is carried out into roughening treatment, being formed increases the tool of surface adhesion force There is the metal level through surface coarsening process of concavo-convex anchor structure；
Step 3）Prepare composite：The high-fire resistance thermoplastic resin adhesives coating device for obtaining is coated through table The unilateral roughening face of the metal level of face roughening treatment, it is after drying process then at a certain temperature that its opposite side coating is high resistance to Hot thermoplastic resin adhesives form sticky surface, remove solvent and press with graphite film, obtain the high-fire resistance graphite of monolayer Film metallic composite.
5. a kind of preparation method of the high-fire resistance graphite film metallic composite as described in any one of claim 1-3, it is special Levy and be：Described method is comprised the following steps；
Step 1）Prepare high-fire resistance thermoplastic resin adhesives：Thermoplastic resin adhesives are dissolved in solvent, are stirred under room temperature Mix to being completely dissolved, add heat filling to stir at a certain temperature, obtain high-fire resistance thermoplastic resin adhesives；
Step 2）Process layer on surface of metal：The both side surface of metal level is carried out roughening treatment, being formed increases surface adhesion force With concavo-convex anchor structure through surface coarsening process metal level；
Step 3）Prepare composite：The high-fire resistance thermoplastic resin adhesives coating device for obtaining is coated through table The roughening face of the upper and lower surface of the metal level of face roughening treatment, after drying process, then is at a certain temperature coated with both sides High-fire resistance thermoplastic resin adhesives form sticky surface, remove solvent and press with graphite film, obtain double-deck high-fire resistance stone Ink film metallic composite.
6. the preparation method of the high-fire resistance graphite film metallic composite according to claim 4 or 5, it is characterised in that： The thermoplastic resin adhesives are TPI class adhesive；The TPI class adhesive is changed by Jing The TPI powder of property is dissolved in high boiling organic solvent and obtains；The high boiling organic solvent is DMAC or DMF Deng.
7. the preparation method of high-fire resistance graphite film metallic composite according to claim 6, it is characterised in that：Step 1）In, in the high-fire resistance thermoplastic resin adhesives, in parts by weight, thermoplastic polyimide resin accounting is 10- 35%；Heat filling accounting is 0.5-14.5%；The solvent accounting is 51-89%.
8. the preparation method of high-fire resistance graphite film metallic composite according to claim 7, it is characterised in that：Step 1）In, in the high-fire resistance thermoplastic resin adhesives, in parts by weight, thermoplastic polyimide resin accounting is 15- 30%；Heat filling accounting is 0.5-10%；The solvent accounting is 65-80%.
9. the preparation method of the high-fire resistance graphite film metallic composite according to claim 4 or 5, it is characterised in that： Step 1）In, the heat filling is the heat conduction such as ultra-fine electrographite powder, Nano graphite powder, CNT, boron nitride, aluminium nitride The one or more of which of filler；The ultra-fine electrographite powder is by broken, grindings of waste material Jing produced in graphite film production etc. Process and be obtained.
10. the preparation method of high-fire resistance graphite film metallic composite according to claim 4, it is characterised in that：Institute The surface thickness for stating coating high-fire resistance thermoplastic resin adhesives formation sticky surface is 2um to 10um；The removing solvent Temperature is 140 DEG C -170 DEG C, and the time for removing solvent is 2min-7min；The temperature of the pressing is 120 DEG C -190 DEG C.
CN201710024795.3A 2017-01-13 2017-01-13 Highly heat-resistant graphite film metal composite and preparation method thereof CN106671501A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107793758A (en) * 2017-11-15 2018-03-13 江苏亚宝绝缘材料股份有限公司 A kind of polymer of CNT compound polyimide resin and its preparation and application
CN111101681A (en) * 2020-01-03 2020-05-05 江苏肯帝亚木业有限公司 High-wear-resistance scratch-resistant carbon nano heat-conducting composite floor

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Publication number Priority date Publication date Assignee Title
CN202213250U (en) * 2011-08-30 2012-05-09 广东生益科技股份有限公司 Graphite-based heatconducting flexible copper-clad plate
CN103144377A (en) * 2013-03-15 2013-06-12 松扬电子材料(昆山)有限公司 Composite electromagnetic-shielding copper clad laminate with heat conduction effect and manufacture method thereof
CN204340308U (en) * 2014-10-17 2015-05-20 合肥傲琪电子科技有限公司 A kind of miniature graphite copper radiating rib

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Publication number Priority date Publication date Assignee Title
CN202213250U (en) * 2011-08-30 2012-05-09 广东生益科技股份有限公司 Graphite-based heatconducting flexible copper-clad plate
CN103144377A (en) * 2013-03-15 2013-06-12 松扬电子材料(昆山)有限公司 Composite electromagnetic-shielding copper clad laminate with heat conduction effect and manufacture method thereof
CN204340308U (en) * 2014-10-17 2015-05-20 合肥傲琪电子科技有限公司 A kind of miniature graphite copper radiating rib

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107793758A (en) * 2017-11-15 2018-03-13 江苏亚宝绝缘材料股份有限公司 A kind of polymer of CNT compound polyimide resin and its preparation and application
CN107793758B (en) * 2017-11-15 2020-08-07 江苏亚宝绝缘材料股份有限公司 Polymer of carbon nano tube composite polyimide resin and preparation and application thereof
CN111101681A (en) * 2020-01-03 2020-05-05 江苏肯帝亚木业有限公司 High-wear-resistance scratch-resistant carbon nano heat-conducting composite floor

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