CN109913185A - A kind of multilayered structure heat-conductive composite material and preparation method thereof containing heat conducting film - Google Patents
A kind of multilayered structure heat-conductive composite material and preparation method thereof containing heat conducting film Download PDFInfo
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Abstract
The invention discloses a kind of multilayered structure heat-conductive composite material and preparation method thereof containing heat conducting film, using epoxy resin as matrix, using the heat conducting film with high heat conductance as heat-conducting medium, compounding filling is carried out using the hexagonal boron nitride and granular heat filling of sheet, pass through stacked in multi-layers, precuring and hot-forming prepare multilayered structure heat-conductive composite material.It is advantageous that the hexagonal boron nitride of sheet is horizontally oriented under hot pressing condition, the thermal conducting path in horizontal direction is constructed together with the heat conducting film that level is sprawled；Another granular heat filling plays bridge joint in system, and the gap between filling six side of sheet nitridation keeps heat conduction network more perfect, while constructing the thermal conducting path in vertical direction.The present invention obtains composite horizontal thermal conductivity and improves 4639%, and vertical thermal conductivity improves 439%, has the advantages that thermal conductivity is high, and thermal stability is good, and dielectric constant and dielectric loss are low, good mechanical performance.
Description
Technical field
The invention belongs to Heat Conduction Material technical field more particularly to a kind of multilayered structure heat-conductive composite materials containing heat conducting film
And preparation method thereof.
Background technique
In recent years, microelectronics is integrated quickly grows with package technique, and electronic equipment is increasingly miniaturized with component, multi-functional
Change, working frequency sharply increases, and the heat that when work generates accumulates rapidly, and environment temperature constantly increases.If the heat of accumulation
The use reliability of equipment and component cannot will be largely effected in time to external diffusion, shortened the working life.It therefore, is guarantee
Equipment and component steadily can efficiently be run, and how be radiated in time as microelectronics Packaging field urgent problem to be solved.
At present, it is common that exported heat in time by the Heat Conduction Material with high thermal conductivity, to guarantee the normal of instrument and equipment
Running.Wherein, thermal-conductive polymer matrix composites are most widely used due to its excellent processability and lower cost.
Epoxy resin is because its excellent electrical insulation capability, thermal property and mechanical performance and moulding process are simple, viscosity
Low, the series of advantages such as curing molding shrinking percentage is small become using polymeric matrix the most universal.But the thermal conductivity of epoxy resin
Rate is lower (0.18 m/W*K), it usually needs heat filling is added to improve the thermal conductivity of composite material.Hexagonal boron nitride (h-
It BN is) a kind of white platelike crystals that structure is similar to graphite, referred to as " white graphite ".H-BN thermal conductivity with higher,
Lower dielectric constant and dielectric loss and excellent electrical insulating property.Therefore the thermally conductive composite wood of hexagonal boron nitride/epoxy resin
The research of material becomes a big hot spot.
A kind of boron nitride/the epoxy announced such as 109280332 A of Chinese invention patent application CN on January 29th, 2019
Resin heat conductive insulating composite material, application for a patent for invention record, which is surface modified boron nitride using silane coupling agent, to be changed
Property, then modified hexagonal boron nitride micro mist and cubic boron nitride micro mist are according to a certain percentage filled epoxy resin.
Modified hexagonal boron nitride and resin matrix interface cohesion are good, the boron nitride of two kinds of different shapes phase interconnection in the base
It connects, constructs thermal conducting path, the heating conduction of composite material has obtained certain promotion.But still there are thermal conductivity promoted amplitude compared with
Small and surface is modified, and there are chemical reagent pollution, not environmentally protective enough problems.Further, since the B-N key of h-BN has portion
The characteristic of sub-key is separated, interlaminar action power is strong, and practical upper surface is modified more difficult, it is however generally that modified effect is unsatisfactory.
H-BN has a significant anisotropic heat conductivity, 20-30 times of horizontal thermally conductive about thickness direction, in differently- oriented directivity it is available compared with
High thermal conductivity.Therefore, orientation process is carried out to hexagonal boron nitride, it is hot to composite material is improved constructs heat conduction network in the base
Conductance is more effective.It is a kind of with high-level thermal conductivity and flexible that we are prepared for the present invention by the method that shear-induced is orientated
Property good thermally conductive alignment films, the high-level thermal conductivity of h-BN and the excellent mechanical properties of epoxy resin are organically combined, introducing is led
Hotting mask and another granular filler construct in horizontal and vertical directions in epoxy matrix as other thermally conductive components
Heat conduction network to reach the thermal conductivity for effectively improving composite material, and improves the purpose of its mechanical performance.
Summary of the invention
The purpose of the present invention is by mechanical shearing induced orientation, stacked in multi-layers and the simple and easy side such as hot-forming
Method constructs heat conduction network structure in epoxy resin-base, prepare it is a kind of there is high heat conductance, and high comprehensive performance contains
The multilayered structure heat-conductive composite material of heat conducting film.
In order to achieve the above purpose, the present invention the following technical schemes are provided:
A kind of multilayered structure heat-conductive composite material containing heat conducting film, by heat conducting film, sheet heat filling, graininess heat filling,
Resin matrix composition, under hot pressing condition, sheet heat filling is orientated in the horizontal direction, and the heat conducting film sprawled with level is in matrix
Thermal conducting path in middle building horizontal direction, graininess heat filling play bridge joint in system, and sheet is thermally conductive fills out for filling
Horizontal heat conduction network is improved in the gap of material, while constructing the thermal conducting path in vertical direction, contributes vertical thermal conductivity.
The heat conducting film is boron nitride heat conducting film, graphene heat conducting film, any one in carbon nanotube heat conducting film, matrix
It is mutually nano-cellulose, polyvinyl alcohol, polyimides, any one in polylactic acid, heat conducting film passes through liquid phase by specific device
Ultrasonic removing, the method preparation of solution blending, mechanical shearing induced orientation, have height-oriented structure, thermal conductivity is high, flexible
Property is good, and the thickness of heat conducting film is uniform, is controlled by mold thickness, and the speed of mechanical shearing is uniform, by apparatus control, fills out in heat conducting film
Expect phase and be capable of forming strong interaction between matrix phase, interface cohesion is good.
The number of plies of the heat conducting film is 0-15 layers, content 0-1.9wt%, and the overall content of heat filling is 10-30wt%,
Resin matrix content is 0-70wt%, and enabling the sum of each component content percentage is 100%.
The sheet heat filling is hexagonal boron nitride h-BN, and partial size is 15-25 μm, and graininess heat filling is nitridation
Aluminium AlN, aluminium oxide Al3O2, silica SiO2, any one in magnesia MgO, partial size is 1-5 μm, and two kinds of fillers add
Adding ratio is (1-3): 1.
The resin matrix also includes curing agent and curing accelerator, and wherein resin matrix is in low viscosity epoxy resin
One kind, curing agent is amine, anhydride, any one in synthetic resin, content 80%-90%, and curing accelerator is
Amine, anhydride, any one in imidazoles, content 1%-3%.
The preparation method of the present invention also provides a kind of multilayered structure heat-conductive composite material containing heat conducting film, including following step
It is rapid:
(1) specific device is utilized, thermally conductive alignment films are prepared by the method for mechanical shearing induced orientation；
(2) a certain amount of liquid epoxy is weighed, then weighs curing agent and curing accelerator in proportion, and is placed on thermostat water bath
Middle heating stirring；
(3) according to (1-3): 1 ratio weighs two kinds of heat fillings, and heat filling is added to the resulting epoxy resin of step 2
In mixture, and in thermostat water bath heating stirring to uniform state；
(4) mechanical hole fabrication is carried out to the resulting heat conducting film of step 1 using porcupine roller, then is placed in the resulting epoxy resin of step 3 and leads
Pre-preg in the homogeneous mixture of hot filler；
(5) in a mold by the homogeneous mixture of heat conducting film and the resulting epoxy resin of step 3 and heat filling after pre-preg
Stacked in multi-layers, then be placed in baking oven and carry out precuring, the material in semisolid is obtained, then transfer them in vulcanizing press,
Carry out hot pressing；
(6) after hot pressing, then sample is transferred in baking oven and is further solidified, finally obtain with multi-layer structure lead
Hot composite material.
At 40-50 DEG C, heating time is 30-50 minutes for the temperature control of thermostat water bath in the step 2.
The heating stirring temperature of heat filling and resin matrix mixture is 40-50 DEG C in the step 3, and mixing time is
2-3 hours.
Its pore size of porcupine roller used in the step 4 and gap are respectively 1-2mm and 2-3mm.
Dip time of the heat conducting film in heat filling and resin matrix mixture is 10-20 minutes in the step 4.
Mold size is side length in the step 5: 30mm, thickness: 2mm.
The temperature of precuring is 90-100 DEG C in the step 5, and pre-cure time is 90-120 minutes, and the temperature of hot pressing is
100-110 DEG C, the pressure of application is 5-10MPa, and hot pressing time is 10-15 minutes；Further cured condition in the step 6
Are as follows: 110-120 DEG C, 2-3h；150-160 DEG C, 4-5h.
The principle of the present invention are as follows:
H-BN is horizontally oriented under hot pressing condition, constructs together with the heat conducting film that level is sprawled thermally conductive logical in horizontal direction
Road, granular heat filling are introduced into system as another component conductive particle, play the role of bridge joint, be filled with h-
Gap between BN lamella keeps heat conduction network more perfect.Further, since h-BN is after being orientated, the thermal conductivity in differently- oriented directivity
It is higher, and it is then very low perpendicular to the thermal conductivity in differently- oriented directivity, and the introducing of granulated filler can make up this defect well,
Contribute the thermal conductivity in vertical direction.
The invention has the advantages that
(1) method of the present invention for preparing heat-conductive composite material is very easy, is made by shear-induced and the method for hot pressing
Filler orientation, significant effect, with other method for alignment, such as induced by magnetic field, electric field induction, vacuum filtration etc. is compared, more simply,
Efficiently.
(2) heat-conductive composite material of the present invention includes a kind of heat conducting film, matrix phase and filler phase shape in the heat conducting film
At chemical bonding, interface cohesion is good, has excellent horizontal thermal conductivity, and flexibility is good.The introducing of heat conducting film facilitates
The building of composite material heat conduction network in the horizontal direction, can effectively improve the horizontal thermal conductivity of composite material.
(3) heat-conductive composite material of the present invention all constructs thermal conducting path in both the horizontal and vertical directions, multiple
The thermal conductivity of condensation material in two directions is all significantly enhanced, and the research of most of heat-conductive composite material is at present
It is directed to the raising of thermal conductivity in a direction.
(4) preparation process of heat-conductive composite material of the present invention is environmentally protective, no chemical solvent pollution, experimental material
It is cheap, it is easy to accomplish large-scale production.
Detailed description of the invention
Fig. 1 show the disconnected of 1 gained BNNS/CNF heat conducting film of embodiment and the heat-conductive composite material containing 6 layers of heat conducting film
Surface scan figure.
Fig. 2 show the infrared spectrogram of 1 gained BNNS/CNF heat conducting film of embodiment.
Fig. 3 show 1,2,3 gained of embodiment and contains its horizontal thermal conductivity of the heat-conductive composite material of different number of plies heat conducting films
With vertical thermal conductivity with the variation of the heat conducting film number of plies.
Fig. 4 show embodiment 1 and the resulting multilayered structure containing heat conducting film of embodiment 4 as a comparison case is thermally conductive multiple
The infrared thermal imaging comparison diagram of condensation material and the heat-conductive composite material without heat conducting film.
Fig. 5 show 2 gained mixed fillers of embodiment filling the multilayered structure heat-conductive composite material containing heat conducting film and
The multilayered structure heat-conductive composite material containing heat conducting film of the resulting single filler filling of embodiment 5 as a comparison case, the two
The comparison diagram of horizontal thermal conductivity and vertical thermal conductivity.
Fig. 6 show heat-conductive composite material of the gained of embodiment 1,2,3 containing different number of plies heat conducting films storage modulus and
Fissipation factor curve graph.
Specific embodiment
Below in conjunction with specific example, technical scheme is described further:
Embodiment 1
With nano-cellulose (CNF) for matrix, hexagonal boron nitride is heat filling, and hexagonal boron nitride is carried out the removing of liquid phase ultrasound
Obtain boron nitride nanosheet (BNNS), then by particular instrument, using the method that shear-induced is orientated prepare boron nitride nanosheet/
Nano-cellulose (BNNS/CNF) thermally conductive alignment films；
According to the ratio of 100:90:1,10g epoxy resin, 9g amine curing agent are weighed, 0.1g imidazoles curing accelerator is placed in
In thermostat water bath, stirred 30 minutes at 45 DEG C；
According to the ratio of 1:1, AlN particle (the i.e. filler that h-BN and 4.1g partial size that 4.1g partial size is 25 μm is 1 μm is weighed respectively
Content is 30wt%), two kinds of fillers are successively added gradually in above-mentioned epoxy resin composition, it is small to continue stirring 3 at 45 DEG C
When；
Mechanical hole fabrication is carried out to the thermally conductive alignment films of BNNS/CNF using porcupine roller, then film is placed in the mixed of above-mentioned epoxy resin and filler
It closes in object pre-preg 15 minutes；
By the alignment films and epoxy resin/filler mixture after pre-preg, it is placed in mold through stacked in multi-layers (6 tunic),
Transfer in baking oven precuring 120 minutes at 90 DEG C；
The sample in semisolid is obtained after precuring, is quickly transferred in vulcanizing press after demoulding, in 100 DEG C, and
Under the pressure of 10MPa, hot pressing 15 minutes；
After hot pressing, then sample is transferred in baking oven and is further solidified, condition of cure are as follows: 110 DEG C, 2h；150 DEG C,
4h finally obtains heat-conductive composite material with multi-layer structure.
Fig. 1 is that the section of 1 gained BNNS/CNF heat conducting film of embodiment and the heat-conductive composite material containing 6 layers of heat conducting film is swept
Tracing, BNNS/CNF heat conducting film has good layer structure as we can see from the figure, and boron nitride nanosheet is made in mechanical shearing
Under firmly, presentation is height-oriented, and heat-conductive composite material has apparent multilayered structure, and heat conducting film is in epoxy matrix along level side
To sprawling.
Fig. 2 is the infrared spectrogram of 1 gained BNNS/CNF heat conducting film of embodiment, be can be seen from map, with BNNS and CNF
It compares, the hydroxyl peak of BNNS/CNF heat conducting film is mobile to lower wave number, illustrates to form hydrogen bond between BNNS and CNF, thus the two
Between interface cohesion it is good.
Embodiment 2
With nano-cellulose (CNF) for matrix, hexagonal boron nitride is heat filling, and hexagonal boron nitride is carried out the removing of liquid phase ultrasound
Obtain boron nitride nanosheet (BNNS), then by particular instrument, using the method that shear-induced is orientated prepare boron nitride nanosheet/
Nano-cellulose (BNNS/CNF) thermally conductive alignment films；
According to the ratio of 100:90:1,10g epoxy resin, 9g amine curing agent are weighed, 0.1g imidazoles curing accelerator is placed in
In thermostat water bath, stirred 30 minutes at 45 DEG C；
According to the ratio of 1:1, AlN particle (the i.e. filler that h-BN and 4.1g partial size that 4.1g partial size is 25 μm is 1 μm is weighed respectively
Content is 30wt%), two kinds of fillers are successively added gradually in above-mentioned epoxy resin composition, it is small to continue stirring 3 at 45 DEG C
When；
Mechanical hole fabrication is carried out to the thermally conductive alignment films of BNNS/CNF using porcupine roller, then film is placed in the mixed of above-mentioned epoxy resin and filler
It closes in object pre-preg 15 minutes；
By the alignment films and epoxy resin/filler mixture after pre-preg, it is placed in mold through stacked in multi-layers (9 tunic),
Transfer in baking oven precuring 120 minutes at 90 DEG C；
The sample in semisolid is obtained after precuring, is quickly transferred in vulcanizing press after demoulding, in 100 DEG C, and
Under the pressure of 10MPa, hot pressing 15 minutes；
After hot pressing, then sample is transferred in baking oven and is further solidified, condition of cure are as follows: 110 DEG C, 2h；150 DEG C,
4h finally obtains heat-conductive composite material with multi-layer structure.
Embodiment 3
With nano-cellulose (CNF) for matrix, hexagonal boron nitride is heat filling, and hexagonal boron nitride is carried out the removing of liquid phase ultrasound
Obtain boron nitride nanosheet (BNNS), then by particular instrument, using the method that shear-induced is orientated prepare boron nitride nanosheet/
Nano-cellulose (BNNS/CNF) thermally conductive alignment films；
According to the ratio of 100:90:1,10g epoxy resin, 9g amine curing agent are weighed, 0.1g imidazoles curing accelerator is placed in
In thermostat water bath, stirred 30 minutes at 45 DEG C；
According to the ratio of 1:1, AlN particle (the i.e. filler that h-BN and 4.1g partial size that 4.1g partial size is 25 μm is 1 μm is weighed respectively
Content is 30wt%), two kinds of fillers are successively added gradually in above-mentioned epoxy resin composition, it is small to continue stirring 3 at 45 DEG C
When；
Mechanical hole fabrication is carried out to the thermally conductive alignment films of BNNS/CNF using porcupine roller, then film is placed in the mixed of above-mentioned epoxy resin and filler
It closes in object pre-preg 15 minutes；
By the alignment films and epoxy resin/filler mixture after pre-preg, it is placed in mold through stacked in multi-layers (12 tunic),
Transfer in baking oven precuring 120 minutes at 90 DEG C；
The sample in semisolid is obtained after precuring, is quickly transferred in vulcanizing press after demoulding, in 100 DEG C, and
Under the pressure of 10MPa, hot pressing 15 minutes；
After hot pressing, then sample is transferred in baking oven and is further solidified, condition of cure are as follows: 110 DEG C, 2h；150 DEG C,
4h finally obtains heat-conductive composite material with multi-layer structure.
Fig. 3 is 1,2,3 gained of embodiment containing its horizontal thermal conductivity of the heat-conductive composite material of different number of plies heat conducting films and hangs down
Directly-heated conductance with the heat conducting film number of plies variation, it can be seen that with the increase of the heat conducting film number of plies, the horizontal thermal conductivity of composite material
It is gradually increased, the variation of vertical thermal conductivity less, but has compared with the thermal conductivity of pure epoxy resin matrix (0.18W/m*K) very big
It improves.
Fig. 4 is the storage modulus and loss of 1,2,3 heat-conductive composite material of the gained containing different number of plies heat conducting films of embodiment
Factor curve figure, as we can see from the figure heat-conductive composite material prepared by the present invention storage modulus with higher, i.e. composite wood
The rigidity of material has compared with pure epoxy resin to be greatly improved, with the increase of the number of plies, the glass transition temperature of composite material
Gradually rise (the corresponding temperature of fissipation factor peak value).
Embodiment 4
As a comparison case
With nano-cellulose (CNF) for matrix, hexagonal boron nitride is heat filling, and hexagonal boron nitride is carried out the removing of liquid phase ultrasound
Obtain boron nitride nanosheet (BNNS), then by particular instrument, using the method that shear-induced is orientated prepare boron nitride nanosheet/
Nano-cellulose (BNNS/CNF) thermally conductive alignment films；
According to the ratio of 100:90:1,10g epoxy resin, 9g amine curing agent are weighed, 0.1g imidazoles curing accelerator is placed in
In thermostat water bath, stirred 30 minutes at 45 DEG C；
Weighing the h-BN(that 8.2g partial size is 25 μm i.e. filer content is 30wt%), filler is added to above-mentioned epoxy resin and is mixed
In object, continue stirring 3 hours at 45 DEG C；
Mechanical hole fabrication is carried out to the thermally conductive alignment films of BNNS/CNF using porcupine roller, then film is placed in the mixed of above-mentioned epoxy resin and filler
It closes in object pre-preg 15 minutes；
By the alignment films and epoxy resin/filler mixture after pre-preg, it is placed in mold through stacked in multi-layers (9 tunic),
Transfer in baking oven precuring 120 minutes at 90 DEG C；
The sample in semisolid is obtained after precuring, is quickly transferred in vulcanizing press after demoulding, in 100 DEG C, and
Under the pressure of 10MPa, hot pressing 15 minutes；
After hot pressing, then sample is transferred in baking oven and is further solidified, condition of cure are as follows: 110 DEG C, 2h；150 DEG C,
4h finally obtains heat-conductive composite material with multi-layer structure.
Fig. 5 is the multilayered structure heat-conductive composite material containing heat conducting film and the implementation of 2 gained mixed fillers of embodiment filling
The multilayered structure heat-conductive composite material containing heat conducting film of the resulting single filler filling of example 4, the horizontal thermal conductivity of the two and vertical
The comparison diagram of thermal conductivity, it is as seen from the figure, more effective to the thermal conductivity for improving composite material using mixed fillers filling, especially
Vertical thermal conductivity, after joined granular aluminium nitride, the vertical thermal conductivity of composite material is significantly improved.
Embodiment 5
As a comparison case
With nano-cellulose (CNF) for matrix, hexagonal boron nitride is heat filling, and hexagonal boron nitride is carried out the removing of liquid phase ultrasound
Obtain boron nitride nanosheet (BNNS), then by particular instrument, using the method that shear-induced is orientated prepare boron nitride nanosheet/
Nano-cellulose (BNNS/CNF) thermally conductive alignment films；
According to the ratio of 100:90:1,10g epoxy resin, 9g amine curing agent are weighed, 0.1g imidazoles curing accelerator is placed in
In thermostat water bath, stirred 30 minutes at 45 DEG C；
According to the ratio of 1:1, AlN particle (the i.e. filler that h-BN and 4.1g partial size that 4.1g partial size is 25 μm is 1 μm is weighed respectively
Content is 30wt%), two kinds of fillers are successively added gradually in above-mentioned epoxy resin composition, it is small to continue stirring 3 at 45 DEG C
When；
Gained mixture is transferred in mold, precuring 120 minutes at 90 DEG C are placed into baking oven；
The sample in semisolid is obtained after precuring, is quickly transferred in vulcanizing press after demoulding, in 100 DEG C, and
Under the pressure of 10MPa, hot pressing 15 minutes；
After hot pressing, then sample is transferred in baking oven and is further solidified, condition of cure are as follows: 110 DEG C, 2h；150 DEG C,
4h finally obtains the heat-conductive composite material for not having multilayered structure.
Fig. 6 (a) and Fig. 6 (b) is embodiment 1 and the resulting thermally conductive composite wood of the multilayered structure containing heat conducting film of embodiment 5
The infrared thermal imaging comparison diagram of material and the heat-conductive composite material without heat conducting film, from comparison diagram as can be seen that containing heat conducting film
Multilayered structure heat-conductive composite material is compared with the heat-conductive composite material without heat conducting film, and temperature changing speed faster, imitate by heat transfer
Fruit is more preferable, illustrates that the introducing of heat conducting film and distinctive multilayered structure are ten on improving heat conductivity in the present invention
Divide effective.
Claims (10)
1. a kind of multilayered structure heat-conductive composite material containing heat conducting film, which is characterized in that by heat conducting film, sheet heat filling,
Granular heat filling, resin matrix composition, under hot pressing condition, sheet heat filling is orientated in the horizontal direction, is sprawled with level
Heat conducting film construct the thermal conducting path in horizontal direction in the base, graininess heat filling plays bridge joint in system,
The gap for filling sheet heat filling, improves horizontal heat conduction network, while constructing the thermal conducting path in vertical direction, and contribution is vertical
Thermal conductivity.
2. the multilayered structure heat-conductive composite material according to claim 1 containing heat conducting film, which is characterized in that the heat conducting film
For any one in boron nitride heat conducting film, graphene heat conducting film, carbon nanotube heat conducting film, matrix is mutually nano-cellulose, gathers
Vinyl alcohol, polyimides, any one in polylactic acid, heat conducting film is total by the removing of liquid phase ultrasound, solution by specific device
Mixed, mechanical shearing induced orientation method preparation, has height-oriented structure, and thermal conductivity is high, and flexibility is good.
3. the multilayered structure heat-conductive composite material according to claim 1 containing heat conducting film, which is characterized in that the heat conducting film
The number of plies be 0-15 layer, content 0-1.9wt%, the overall content of heat filling is 10-30wt%, and resin matrix content is 0-
70wt%, enabling the sum of each component content percentage is 100%.
4. the multilayered structure heat-conductive composite material according to claim 1 containing heat conducting film, which is characterized in that the sheet
Heat filling is hexagonal boron nitride h-BN, and partial size is 15-25 μm, and graininess heat filling is aluminium nitride AlN, aluminium oxide Al3O2、
Silica SiO2, any one in magnesia MgO, partial size is 1-5 μm, and the adding proportion of two kinds of fillers is (1-3): 1.
5. the multilayered structure heat-conductive composite material according to claim 1 containing heat conducting film, which is characterized in that the resin
Matrix also includes curing agent and curing accelerator, and wherein resin matrix is one of low viscosity epoxy resin, and curing agent is amine
Class, anhydride, any one in synthetic resin, content 80%-90%, curing accelerator is amine, anhydride, imidazoles
In any one, content 1%-3%.
6. a kind of preparation method of the multilayered structure heat-conductive composite material containing heat conducting film, which comprises the following steps:
(1) specific device is utilized, thermally conductive alignment films are prepared by the method for mechanical shearing induced orientation；
(2) a certain amount of liquid epoxy is weighed, then weighs curing agent and curing accelerator in proportion, and is placed on thermostat water bath
Middle heating stirring；
(3) according to (1-3): 1 ratio weighs two kinds of heat fillings, and heat filling is added to the resulting epoxy resin of step 2
In mixture, and in thermostat water bath heating stirring to uniform state；
(4) mechanical hole fabrication is carried out to the resulting heat conducting film of step 1 using porcupine roller, then is placed in the resulting epoxy resin of step 3 and leads
Pre-preg in the homogeneous mixture of hot filler；
(5) in a mold by the homogeneous mixture of heat conducting film and the resulting epoxy resin of step 3 and heat filling after pre-preg
Stacked in multi-layers, then be placed in baking oven and carry out precuring, the material in semisolid is obtained, then transfer them in vulcanizing press,
Carry out hot pressing；
(6) after hot pressing, then sample is transferred in baking oven and is further solidified, finally obtain with multi-layer structure lead
Hot composite material.
7. preparation method according to claim 6, which is characterized in that the temperature control of thermostat water bath in the step 2
At 40-50 DEG C, heating time is 30-50 minutes.
8. preparation method according to claim 6, which is characterized in that heat filling and resin matrix are mixed in the step 3
The heating stirring temperature for closing object is 40-50 DEG C, and mixing time is 2-3 hours.
9. preparation method according to claim 6, which is characterized in that heat conducting film is in heat filling and tree in the step 4
Dip time in rouge substrate mixture is 10-20 minutes.
10. preparation method according to claim 6, which is characterized in that the temperature of precuring is 90-100 in the step 5
DEG C, pre-cure time is 90-120 minutes, and the temperature of hot pressing is 100-110 DEG C, and the pressure of application is 5-10MPa, hot pressing time
It is 10-15 minutes；Further cured condition in the step 6 are as follows: 110-120 DEG C, 2-3h；150-160 DEG C, 4-5h.
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