CN106751526A - A kind of epoxy resin heat conduction composite and its preparation and application - Google Patents
A kind of epoxy resin heat conduction composite and its preparation and application Download PDFInfo
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- CN106751526A CN106751526A CN201611244696.8A CN201611244696A CN106751526A CN 106751526 A CN106751526 A CN 106751526A CN 201611244696 A CN201611244696 A CN 201611244696A CN 106751526 A CN106751526 A CN 106751526A
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- epoxy resin
- inorganic filler
- heat conduction
- conduction composite
- dimensional slice
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- 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
- C08K3/38—Boron-containing compounds
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- 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
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/08—Oxygen-containing compounds
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- 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
- C08K3/38—Boron-containing compounds
- C08K2003/382—Boron-containing compounds and nitrogen
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- 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
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
- C08L2203/206—Applications use in electrical or conductive gadgets use in coating or encapsulating of electronic parts
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Abstract
The invention discloses a kind of epoxy resin heat conduction composite and its preparation and application, wherein, the epoxy resin heat conduction composite is the inorganic filler for being dispersed with volume ratio 5% to 20% in the epoxy, and the inorganic filler includes two-dimensional slice inorganic filler and spherical inorganic filler.The present invention is improved by heat filling structure and addition crucial in the epoxy resin heat conduction composite etc., and use corresponding preparation method, can effectively solve the problem that epoxy resin composite material heat conductivility is not good compared with prior art, the problem of viscosity grade high, addition is combined by the heat filling of variety classes and pattern, prepare and have high-termal conductivity, low-viscosity epoxy resin base heat-conductive composite material concurrently, be particularly suitable for use as electronic package material.
Description
Technical field
The invention belongs to thermal interfacial material field, more particularly, to a kind of epoxy resin heat conduction composite and its system
It is standby with application.
Background technology
Nowadays the use of electronic product becomes increasingly prevalent, while also the direction towards miniaturization is developed, it should
Used time can produce substantial amounts of heat, and the rising of electronic device temperature can all have very big to life-span, efficiency and power consumption aspect
Influence, therefore improve focus of the heat-sinking capability as research work.Heat conductive insulating encapsulating material with high heat dispersion is to carry
The key link of electronic component job stability high and service life.Plastic Package is with its excellent electrical insulation capability, processing
Performance is widely used in thermal interfacial material and Electronic Packaging field with cost advantage, and its epoxy resin is due to shrinkage factor
Low, adhesive property is good, corrosion resistance and good the advantages of, account for more than the 90% of plastic encapsulant.But epoxy resin thermal conductivity
Can be poor, cause electronic element radiating difficult, easily aging, service life is short.
Can be with to the inorganic filler (such as aluminum oxide, aluminium nitride, boron nitride, magnesia) that high heat conductance is added in epoxy resin
The effective thermal conductivity for improving matrix material.But generally need just significantly improve composite thermal conductivity in loading very high
Rate.The mechanical property and processing characteristics that the high filler loading capacity of inorganic filler result in composite decline to a great extent.Specifically, this will
Cause the high viscosity of epoxy resin composite system, it is difficult to effectively carry out the encapsulation of electronic component.
Under this background, studying a kind of epoxy resin-base composite material with low viscosity and high heat conduction characteristic just has weight
Big science and practical value.
The content of the invention
For the disadvantages described above or Improvement requirement of prior art, it is an object of the invention to provide a kind of epoxy resin heat conduction
Composite and its preparation and application, wherein by heat filling structure crucial in the epoxy resin heat conduction composite,
And addition etc. is improved, and corresponding preparation method is used, epoxy resin is can effectively solve the problem that compared with prior art
Composite heat conductivility is not good, the problem of viscosity grade high, and addition is combined by the heat filling of variety classes and pattern, prepares
Have the epoxy resin based thermal conductive composite of low viscosity and high heat conduction characteristic concurrently；It is inorganic in the epoxy resin heat conduction composite
The volume ratio of filler addition as little as 5% to 20%, and thermal conductivity factor is not less than 0.91W/mK, its viscosity is small at 30 DEG C
In 20Pas, thermal conductivity is good, and viscosity is low, it is ensured that prepared by the good mechanical property of the composite and processing characteristics, especially fit
For as electronic package material.
To achieve the above object, according to one aspect of the present invention, there is provided a kind of epoxy resin heat conduction composite, its
It is characterised by, the inorganic filler of volume ratio 5% to 20% is dispersed with the epoxy, and the inorganic filler includes two-dimensional slice
Layer inorganic filler and spherical inorganic filler.
Used as present invention further optimization, the average grain diameter of the two-dimensional slice inorganic filler is at 10 microns to 40 microns
Between, the average grain diameter of the spherical inorganic filler is between 5 microns to 40 microns.
As present invention further optimization, the volume ratio of the two-dimensional slice inorganic filler and the spherical inorganic filler
4:1 to 1:Between 1.
Used as present invention further optimization, the inorganic filler is aluminum oxide, boron nitride, aluminium nitride, magnesia, oxidation
At least one in zinc, silica.
Used as present invention further optimization, the epoxy resin is bisphenol A-type or bisphenol f type epoxy resin.
Used as present invention further optimization, the thermal conductivity factor of the epoxy resin heat conduction composite is not less than 0.91W/
MK, its viscosity is less than 20Pas at 30 DEG C.
It is another aspect of this invention to provide that the invention provides the side prepared such as above-mentioned epoxy resin heat conduction composite
Method, it is characterised in that comprise the following steps：
(1) two-dimensional slice inorganic filler and spherical inorganic filler are pressed 4:1 to 1:1 volume ratio carries out dispensing, fully dry
Uniform mixing, obtains mixed fillers after dry；
(2) mixed fillers in step (1) are added in epoxy resin, dispersed, de-bubbled solidify afterwards obtain
The epoxy resin heat conduction composite.
As present invention further optimization, in the step (2), it is described it is dispersed be using ultrasonic disperse and high speed
The method of stirring so that the mixed fillers are dispersed in epoxy resin-base material；Preferably, the high-speed stirred institute
The rotating speed of use is not less than 1000 rpms.
According to another aspect of the present invention, the invention provides above-mentioned epoxy resin heat conduction composite as Electronic Packaging
The application of material.
In general, by the contemplated above technical scheme of the present invention compared with prior art, can obtain down and show
Beneficial effect：
(1) present invention is provided two-dimensional slice inorganic filler and spherical inorganic filler modified epoxy resin composite, by
Compound system viscosity can be effectively reduced after Ball-type packing has more preferable mobility, Ball-type packing to add in the base, so that
The viscosity of epoxy resin composite material is reduced while raising system thermal conductivity.
Two-dimensional slice inorganic filler of the present invention, average grain diameter (that is, two-dimensional slice between 10 microns to 40 microns
Maximum length is between 10 microns to 40 microns in the slice plane of layer inorganic filler), the thickness of the two-dimensional slice inorganic filler
The length and width an order of magnitude less than slice plane is at least needed, for example, can be 100nm to 800nm.
(2) present invention is provided two-dimensional slice inorganic filler and spherical inorganic filler modified epoxy resin composite, by
In epoxy resin is filled into after the filler of different-shape mixes in proper proportions, the dispersiveness of system filler is optimized, from
And the viscosity of compound system is reduced, improve processing characteristics.
(3) present invention is provided two-dimensional slice inorganic filler and spherical inorganic filler modified epoxy resin composite, two
Dimension lamella inorganic filler is mainly constructs passage of heat formation heat conduction network, and the addition of Ball-type packing shows obvious association
Same effect, improves the interaction between filler and epoxy resin-base, is dropped building while effective heat conduction threshold oozes network
Low system viscosity, realizes that heat conductivility is greatly improved.
(4) composite material and preparation method thereof that the present invention is provided, step is simple, and reaction condition is gentle, is adapted to industry big
Large-scale production.
(5) present invention is provided two-dimensional slice inorganic filler and spherical inorganic filler modified epoxy resin composite, should
For thermal interfacial material, thermal conductivity can be strengthened, submit heat exchanger effectiveness to.It is particularly suitable for electronic package material, such as collecting
Into circuit board package etc., electronic element radiating performance can be greatly improved on the premise of processing characteristics is ensured, delay electronic component
Heat ageing simultaneously ensures its job stability, so as to extend the service life of electronic product.
Preferred scheme, by adjusting the mixed proportion of two-dimensional slice inorganic filler and spherical inorganic filler, adjusts described multiple
The processing characteristics and heat conductivility of condensation material.
Preferred scheme, by adjusting epoxy resin and curing agent type, adjusts the condition of cure of the composite, so that
Meet the particular/special requirement of different construction sites.
Preferred scheme, by selecting different types of epoxy resin so that the composite has different processabilities
Energy and physical and chemical performance, meet different industrial requirements.
Brief description of the drawings
Fig. 1 be in the embodiment of the present invention 1,2,4,5,6,7 37 microns of boron nitride pieces and 40 microns of ball-aluminium oxides by difference
The viscosity comparison diagram of the epoxy resin composite material that proportioning is obtained；
Fig. 2 be in the embodiment of the present invention 1,2,3,7 37 microns of boron nitride pieces and 40 microns of ball-aluminium oxides by different ratio
The viscosity comparison diagram of the epoxy resin composite material for obtaining；
Fig. 3 be in the embodiment of the present invention 1,2,3,4,5,6,7 37 microns of boron nitride pieces and 40 microns of ball-aluminium oxides by not
The thermal conductivity comparison diagram of the epoxy resin composite material for obtaining is matched together；
Fig. 4 is 37 microns of boron nitride pieces and 40 microns of spherical aluminum oxide epoxy resin composite materials in the embodiment of the present invention 7
Profile scanning electron microscope.
Specific embodiment
In order to make the purpose , technical scheme and advantage of the present invention be clearer, it is right below in conjunction with drawings and Examples
The present invention is further elaborated.It should be appreciated that specific embodiment described herein is only used to explain the present invention, not
For limiting the present invention.As long as additionally, technical characteristic involved in invention described below each implementation method that
Conflict is not constituted between this can be just mutually combined.
The epoxy resin composite material that the present invention is provided, it is dispersed in the epoxy to have volume ratio 5% to 20%
Inorganic filler, the inorganic filler includes two-dimensional slice inorganic filler and spherical inorganic filler, and (these inorganic fillers can be from
In the market is bought), the average grain diameter of the two-dimensional slice inorganic filler between 10 microns to 40 microns, fill out by the inorganic spherical
The average grain diameter of material between 5 microns to 40 microns, the volume ratio of the two-dimensional slice inorganic filler and spherical inorganic filler
4:1 to 1:Between 1.Preferably, the average grain diameter of the two-dimensional slice inorganic filler is described spherical at 30 microns to 40 microns
The average grain diameter of inorganic filler at 30 microns to 40 microns, the volume ratio of the two-dimensional slice inorganic filler and spherical inorganic filler
2:1 to 1:Between 1.
The inorganic filler can be the one kind in aluminum oxide, boron nitride, aluminium nitride, magnesia, zinc oxide, silica
Or two kinds, one or two preferably in aluminum oxide, boron nitride, aluminium nitride.
The epoxy resin composite material that the present invention is provided, its heat conductivility is tested according to testing standard ASTMC1113, heat conduction
Coefficient is not less than 0.91W/mK, and its viscosity is less than 20Pas at 30 DEG C.
The present invention carries common epoxy resin composite material, according to formula rate, can be according to general filler adding method
Prepare, preferably prepare by the following method：
(1) two-dimensional slice inorganic filler and the spherical inorganic filler of formula rate are taken, is uniformly mixed after fully drying, obtained
Mixed fillers.
(2) mixed fillers obtained in step (1) are added in epoxy resin, dispersed, de-bubbled solidify afterwards, i.e.,
Obtain the epoxy resin composite material.Preferably, described epoxy resin is bisphenol A-type or bisphenol f type epoxy resin；It is described
Curing agent be imidazoles and/or acid anhydride type curing agent, the addition of curing agent is 6~90wt.% of epoxy resin.
The detailed process of wherein step (2) is as follows：
(2-1) disperses：The mixed fillers obtained in step (1) are added in epoxy resin, ultrasonic wave disperses or machine
Tool is stirred and causes uniform filling dispersion, obtains epoxy resin/filler dispersion system.Preferably, the ultrasonic disperse power is preferred
For：200 watts, temperature is 50 DEG C -70 DEG C, ultrasonic disperse 0.5-2 hours；The high-speed stirred is：40 DEG C -70 DEG C, 600-2000
Rev/min, stir 1-2 hours.
After (2-2) is by the epoxy resin obtained by step (2-1)/filler dispersion system vacuum abjection bubble, curing agent is added,
And further high-speed stirred and abjection bubble, obtain modified epoxy dispersion.The high-speed stirred and abjection bubble mistake
Cheng Caiyong rotations/revolution mixer, high-speed stirred speed is 1600~1900 rpms, and the rotating speed during abjection bubble is
2000~2100 rpms.
The modified epoxy dispersion that step (2-2) is obtained is carried out curing reaction by (2-3), that is, obtain the epoxy
Resin composite materials.
The solidification process includes low temperature precuring and hot setting；Precuring temperature is 60 DEG C~100 DEG C, during precuring
Between be 1~2 hour；Hot setting temperature is 150 DEG C~180 DEG C, and high temperature pre-cure time is 4~7 hours.
The epoxy resin composite material that the present invention is provided, while heat conductivility is ensured, with good machining
Performance, viscosity is tested according to testing standard Anton Paar MCR302, and 20Pas is less than at 30 DEG C, is suitable for electronic seal
Package material.
It is below specific embodiment：
Embodiment 1
A kind of epoxy resin composite material, the in the epoxy dispersed inorganic filler for having a volume ratio 12%, institute
Stating inorganic filler includes two-dimensional slice inorganic filler, and the average grain diameter of the two-dimensional slice inorganic filler is 37 microns, described two
The inorganic filler of dimension lamella is boron nitride.The epoxy resin composite material, its heat conductivility is according to testing standard ASTM C1113
Test, thermal conductivity factor is 0.81W/mK, and its viscosity is 7.8Pas at 30 DEG C.
A kind of epoxy resin composite material, according to formula rate, prepares by the following method：
(1) two-dimensional slice inorganic filler is taken, abundant dried filler.
(2) the two-dimensional slice inorganic filler obtained in step (1) is added in epoxy resin, dispersed, de-bubbled
Solidify afterwards, that is, obtain the epoxy resin composite material.Described epoxy resin is bisphenol A type epoxy resin；Described solidification
Agent is imidazoles and acid anhydride type curing agent, and the addition of acid anhydride type curing agent is the 85wt.% of epoxy resin, imidazole curing agent
Addition for epoxy resin 1wt.%.
The detailed process of wherein step (2) is as follows：
(2-1) disperses：The filler obtained in step (1) is added in epoxy resin, ultrasonic wave dispersion or machinery are stirred
Mix so that uniform filling dispersion, obtains epoxy resin/filler dispersion system.Mechanical agitation speed is 800 rpms, during stirring
Between be 2 hours；Ultrasonic dispersing time is 1 hour.
After (2-2) is by the epoxy resin obtained by step (2-1)/filler dispersion system vacuum abjection bubble, curing agent is added,
And further high-speed stirred and abjection bubble, obtain modified epoxy dispersion.The high-speed stirred and abjection bubble mistake
Cheng Caiyong rotations/revolution mixer, high-speed stirred 3 minutes, speed is 1600 rpms, abjection bubble process 2 minutes, rotating speed
It is 2000 rpms.
The modified epoxy dispersion that step (2-2) is obtained is carried out curing reaction by (2-3), that is, obtain the epoxy
Resin composite materials.
The solidification process includes low temperature precuring and hot setting；Precuring temperature is 60 DEG C, and pre-cure time is 2 small
When；Hot setting temperature is 150 DEG C, and high temperature pre-cure time is 5 hours.
Embodiment 2
A kind of epoxy resin composite material, the in the epoxy dispersed inorganic filler for having a volume ratio 15%, institute
Stating inorganic filler includes two-dimensional slice inorganic filler, and the average grain diameter of the two-dimensional slice inorganic filler is 37 microns, described two
The inorganic filler of dimension lamella is boron nitride.The epoxy resin composite material, its heat conductivility is according to testing standard ASTM C1113
Test, thermal conductivity factor is 1.01W/mK, and its viscosity is 12.8Pas at 30 DEG C.
A kind of epoxy resin composite material, according to formula rate, prepares by the following method：
(1) two-dimensional slice inorganic filler is taken, abundant dried filler.
(2) the two-dimensional slice inorganic filler obtained in step (1) is added in epoxy resin, dispersed, de-bubbled
Solidify afterwards, that is, obtain the epoxy resin composite material.Described epoxy resin is bisphenol A type epoxy resin；Described solidification
Agent is imidazoles and acid anhydride type curing agent, and the addition of acid anhydride type curing agent is the 85wt.% of epoxy resin, imidazole curing agent
Addition for epoxy resin 1wt.%.
The detailed process of wherein step (2) is as follows：
(2-1) disperses：The filler obtained in step (1) is added in epoxy resin, ultrasonic wave dispersion or machinery are stirred
Mix so that uniform filling dispersion, obtains epoxy resin/filler dispersion system.Mechanical agitation speed is 800 rpms, during stirring
Between be 2 hours；Ultrasonic dispersing time is 1 hour.
After (2-2) is by the epoxy resin obtained by step (2-1)/filler dispersion system vacuum abjection bubble, curing agent is added,
And further high-speed stirred and abjection bubble, obtain modified epoxy dispersion.The high-speed stirred and abjection bubble mistake
Cheng Caiyong rotations/revolution mixer, high-speed stirred 3 minutes, speed is 1600 rpms, abjection bubble process 2 minutes, rotating speed
It is 2000 rpms.
The modified epoxy dispersion that step (2-2) is obtained is carried out curing reaction by (2-3), that is, obtain the epoxy
Resin composite materials.
The solidification process includes low temperature precuring and hot setting；Precuring temperature is 60 DEG C, and pre-cure time is 2 small
When；Hot setting temperature is 150 DEG C, and high temperature pre-cure time is 5 hours.
Embodiment 3
A kind of epoxy resin composite material, the in the epoxy dispersed inorganic filler for having a volume ratio 18%, institute
Stating inorganic filler includes two-dimensional slice inorganic filler, and the average grain diameter of the two-dimensional slice inorganic filler is 37 microns, described two
The inorganic filler of dimension lamella is boron nitride.The epoxy resin composite material, its heat conductivility is according to testing standard ASTM C1113
Test, thermal conductivity factor is 1.09W/mK, and its viscosity is 42.8Pas at 30 DEG C.
A kind of epoxy resin composite material, according to formula rate, prepares by the following method：
(1) two-dimensional slice inorganic filler is taken, abundant dried filler.
(2) the two-dimensional slice inorganic filler obtained in step (1) is added in epoxy resin, dispersed, de-bubbled
Solidify afterwards, that is, obtain the epoxy resin composite material.Described epoxy resin is bisphenol A type epoxy resin；Described solidification
Agent is imidazoles and acid anhydride type curing agent, and the addition of acid anhydride type curing agent is the 85wt.% of epoxy resin, imidazole curing agent
Addition for epoxy resin 1wt.%.
The detailed process of wherein step (2) is as follows：
(2-1) disperses：The filler obtained in step (1) is added in epoxy resin, ultrasonic wave dispersion or machinery are stirred
Mix so that uniform filling dispersion, obtains epoxy resin/filler dispersion system.Mechanical agitation speed is 800 rpms, during stirring
Between be 2 hours；Ultrasonic dispersing time is 1 hour.
After (2-2) is by the epoxy resin obtained by step (2-1)/filler dispersion system vacuum abjection bubble, curing agent is added,
And further high-speed stirred and abjection bubble, obtain modified epoxy dispersion.The high-speed stirred and abjection bubble mistake
Cheng Caiyong rotations/revolution mixer, high-speed stirred 3 minutes, speed is 1600 rpms, abjection bubble process 2 minutes, rotating speed
It is 2000 rpms.
The modified epoxy dispersion that step (2-2) is obtained is carried out curing reaction by (2-3), that is, obtain the epoxy
Resin composite materials.
The solidification process includes low temperature precuring and hot setting；Precuring temperature is 60 DEG C, and pre-cure time is 2 small
When；Hot setting temperature is 150 DEG C, and high temperature pre-cure time is 5 hours.
Embodiment 4
A kind of epoxy resin composite material, the in the epoxy dispersed inorganic filler for having a volume ratio 15%, institute
Stating inorganic filler includes two-dimensional slice inorganic filler and spherical inorganic filler, and the average grain diameter of the two-dimensional slice inorganic filler is
37 microns, the average grain diameter of the spherical inorganic filler is 40 microns, the two-dimensional slice inorganic filler and spherical inorganic filler
Volume ratio be 4:1.The two-dimensional slice inorganic filler is boron nitride；The spherical inorganic filler is aluminum oxide.
The epoxy resin composite material, its heat conductivility is tested according to testing standard ASTM C1113, and thermal conductivity factor is
0.91W/mK, its viscosity is tested according to testing standard Anton Paar MCR302, is 8.9Pas at 30 DEG C.
A kind of epoxy resin composite material, according to formula rate, prepares by the following method：
(1) two-dimensional slice inorganic filler and the spherical inorganic filler of formula rate are taken, is uniformly mixed after fully drying, obtained
Mixed fillers.
(2) mixed fillers obtained in step (1) are added in epoxy resin, dispersed, de-bubbled solidify afterwards, i.e.,
Obtain the epoxy resin composite material.Described epoxy resin is bisphenol A type epoxy resin；Described curing agent is imidazoles
And acid anhydride type curing agent, the addition of acid anhydride type curing agent is the 85wt.% of epoxy resin, and the addition of imidazole curing agent is
The 1wt.% of epoxy resin.
The detailed process of wherein step (2) is as follows：
(2-1) disperses：The mixed fillers obtained in step (1) are added in epoxy resin, ultrasonic wave disperses or machine
Tool is stirred and causes uniform filling dispersion, obtains epoxy resin/filler dispersion system.Mechanical agitation speed is 800 rpms, is stirred
The time is mixed for 2 hours；Ultrasonic dispersing time is 1 hour.
After (2-2) is by the epoxy resin obtained by step (2-1)/filler dispersion system vacuum abjection bubble, curing agent is added,
And further high-speed stirred and abjection bubble, obtain modified epoxy dispersion.The high-speed stirred and abjection bubble mistake
Cheng Caiyong rotations/revolution mixer, high-speed stirred speed is 1600 rpms, and the rotating speed during abjection bubble is 2000 turns
It is per minute.
The modified epoxy dispersion that step (2-2) is obtained is carried out curing reaction by (2-3), that is, obtain the epoxy
Resin composite materials.
The solidification process includes low temperature precuring and hot setting；Precuring temperature is 60 DEG C, and pre-cure time is 2 small
When；Hot setting temperature is 150 DEG C, and high temperature pre-cure time is 5 hours.
Embodiment 5
A kind of epoxy resin composite material, the in the epoxy dispersed inorganic filler for having a volume ratio 18%, institute
Stating inorganic filler includes two-dimensional slice inorganic filler and spherical inorganic filler, and the average grain diameter of the two-dimensional slice inorganic filler is
37 microns, the average grain diameter of the spherical inorganic filler is 40 microns, the two-dimensional slice inorganic filler and spherical inorganic filler
Volume ratio be 2:1.The two-dimensional slice inorganic filler is boron nitride；The spherical inorganic filler is aluminum oxide.
The epoxy resin composite material, its heat conductivility is tested according to testing standard ASTM C1113, and thermal conductivity factor is
1.06W/mK, its viscosity is tested according to testing standard Anton Paar MCR302, is 11.2Pas at 30 DEG C.
A kind of epoxy resin composite material, according to formula rate, prepares by the following method：
(1) two-dimensional slice inorganic filler and the spherical inorganic filler of formula rate are taken, is uniformly mixed after fully drying, obtained
Mixed fillers.
(2) mixed fillers obtained in step (1) are added in epoxy resin, dispersed, de-bubbled solidify afterwards, i.e.,
Obtain the epoxy resin composite material.Described epoxy resin is bisphenol A type epoxy resin；Described curing agent is imidazoles
And acid anhydride type curing agent, the addition of acid anhydride type curing agent is the 85wt.% of epoxy resin, and the addition of imidazole curing agent is
The 1wt.% of epoxy resin.
The detailed process of wherein step (2) is as follows：
(2-1) disperses：The mixed fillers obtained in step (1) are added in epoxy resin, ultrasonic wave disperses or machine
Tool is stirred and causes uniform filling dispersion, obtains epoxy resin/filler dispersion system.Mechanical agitation speed is 800 rpms, is stirred
The time is mixed for 2 hours；Ultrasonic dispersing time is 1 hour.
After (2-2) is by the epoxy resin obtained by step (2-1)/filler dispersion system vacuum abjection bubble, curing agent is added,
And further high-speed stirred and abjection bubble, obtain modified epoxy dispersion.The high-speed stirred and abjection bubble mistake
Cheng Caiyong rotations/revolution mixer, high-speed stirred speed is 1600 rpms, and the rotating speed during abjection bubble is 2000 turns
It is per minute.
The modified epoxy dispersion that step (2-2) is obtained is carried out curing reaction by (2-3), that is, obtain the epoxy
Resin composite materials.
The solidification process includes low temperature precuring and hot setting；Precuring temperature is 60 DEG C, and pre-cure time is 2 small
When；Hot setting temperature is 150 DEG C, and high temperature pre-cure time is 5 hours.
Embodiment 6
A kind of epoxy resin composite material, the in the epoxy dispersed inorganic filler for having a volume ratio 21%, institute
Stating inorganic filler includes two-dimensional slice inorganic filler and spherical inorganic filler, and the average grain diameter of the two-dimensional slice inorganic filler is
37 microns, the average grain diameter of the spherical inorganic filler is 40 microns, the two-dimensional slice inorganic filler and spherical inorganic filler
Volume ratio be 4:3.The two-dimensional slice inorganic filler is boron nitride；The spherical inorganic filler is aluminum oxide.
The epoxy resin composite material, its heat conductivility is tested according to testing standard ASTM C1113, and thermal conductivity factor is
1.16W/mK, its viscosity is tested according to testing standard Anton Paar MCR302, is 12.2Pas at 30 DEG C.
A kind of epoxy resin composite material, according to formula rate, prepares by the following method：
(1) two-dimensional slice inorganic filler and the spherical inorganic filler of formula rate are taken, is uniformly mixed after fully drying, obtained
Mixed fillers.
(2) mixed fillers obtained in step (1) are added in epoxy resin, dispersed, de-bubbled solidify afterwards, i.e.,
Obtain the epoxy resin composite material.Described epoxy resin is bisphenol A type epoxy resin；Described curing agent is imidazoles
And acid anhydride type curing agent, the addition of acid anhydride type curing agent is the 85wt.% of epoxy resin, and the addition of imidazole curing agent is
The 1wt.% of epoxy resin.
The detailed process of wherein step (2) is as follows：
(2-1) disperses：The mixed fillers obtained in step (1) are added in epoxy resin, ultrasonic wave disperses or machine
Tool is stirred and causes uniform filling dispersion, obtains epoxy resin/filler dispersion system.Mechanical agitation speed is 800 rpms, is stirred
The time is mixed for 2 hours；Ultrasonic dispersing time is 1 hour.
After (2-2) is by the epoxy resin obtained by step (2-1)/filler dispersion system vacuum abjection bubble, curing agent is added,
And further high-speed stirred and abjection bubble, obtain modified epoxy dispersion.The high-speed stirred and abjection bubble mistake
Cheng Caiyong rotations/revolution mixer, high-speed stirred speed is 1600 rpms, and the rotating speed during abjection bubble is 2000 turns
It is per minute.
The modified epoxy dispersion that step (2-2) is obtained is carried out curing reaction by (2-3), that is, obtain the epoxy
Resin composite materials.
The solidification process includes low temperature precuring and hot setting；Precuring temperature is 60 DEG C, and pre-cure time is 2 small
When；Hot setting temperature is 150 DEG C, and high temperature pre-cure time is 5 hours.
Embodiment 7
A kind of epoxy resin composite material, the in the epoxy dispersed inorganic filler for having a volume ratio 24%, institute
Stating inorganic filler includes two-dimensional slice inorganic filler and spherical inorganic filler, and the average grain diameter of the two-dimensional slice inorganic filler is
37 microns, the average grain diameter of the spherical inorganic filler is 40 microns, the two-dimensional slice inorganic filler and spherical inorganic filler
Volume ratio be 1:1.The two-dimensional slice inorganic filler is boron nitride；The spherical inorganic filler is aluminum oxide.
The epoxy resin composite material, its heat conductivility is tested according to testing standard ASTM C1113, and thermal conductivity factor is
1.26W/mK, its viscosity is tested according to testing standard Anton Paar MCR302, is 16.2Pas at 30 DEG C.
A kind of epoxy resin composite material, according to formula rate, prepares by the following method：
(1) two-dimensional slice inorganic filler and the spherical inorganic filler of formula rate are taken, is uniformly mixed after fully drying, obtained
Mixed fillers.
(2) mixed fillers obtained in step (1) are added in epoxy resin, dispersed, de-bubbled solidify afterwards, i.e.,
Obtain the epoxy resin composite material.Described epoxy resin is bisphenol A type epoxy resin；Described curing agent is imidazoles
And acid anhydride type curing agent, the addition of acid anhydride type curing agent is the 85wt.% of epoxy resin, and the addition of imidazole curing agent is
The 1wt.% of epoxy resin.
The detailed process of wherein step (2) is as follows：
(2-1) disperses：The mixed fillers obtained in step (1) are added in epoxy resin, ultrasonic wave disperses or machine
Tool is stirred and causes uniform filling dispersion, obtains epoxy resin/filler dispersion system.Mechanical agitation speed is 800 rpms, is stirred
The time is mixed for 2 hours；Ultrasonic dispersing time is 1 hour.
After (2-2) is by the epoxy resin obtained by step (2-1)/filler dispersion system vacuum abjection bubble, curing agent is added,
And further high-speed stirred and abjection bubble, obtain modified epoxy dispersion.The high-speed stirred and abjection bubble mistake
Cheng Caiyong rotations/revolution mixer, high-speed stirred speed is 1600 rpms, and the rotating speed during abjection bubble is 2000 turns
It is per minute.
The modified epoxy dispersion that step (2-2) is obtained is carried out curing reaction by (2-3), that is, obtain the epoxy
Resin composite materials.
The solidification process includes low temperature precuring and hot setting；Precuring temperature is 60 DEG C, and pre-cure time is 2 small
When；Hot setting temperature is 150 DEG C, and high temperature pre-cure time is 5 hours.
Embodiment 8
A kind of epoxy resin composite material, the in the epoxy dispersed inorganic filler for having a volume ratio 24%, institute
Stating inorganic filler includes two-dimensional slice inorganic filler and spherical inorganic filler, and the average grain diameter of the two-dimensional slice inorganic filler is
37 microns, the average grain diameter of the spherical inorganic filler is 40 microns, the two-dimensional slice inorganic filler and spherical inorganic filler
Volume ratio be 1:1.The two-dimensional slice inorganic filler is boron nitride；The spherical inorganic filler is aluminum oxide.
The epoxy resin composite material, its heat conductivility is tested according to testing standard ASTM C1113, and thermal conductivity factor is
1.26W/mK, its viscosity is tested according to testing standard Anton Paar MCR302, is 16.2Pas at 30 DEG C.
A kind of epoxy resin composite material, according to formula rate, prepares by the following method：
(1) two-dimensional slice inorganic filler and the spherical inorganic filler of formula rate are taken, is uniformly mixed after fully drying, obtained
Mixed fillers.
(2) mixed fillers obtained in step (1) are added in epoxy resin, dispersed, de-bubbled solidify afterwards, i.e.,
Obtain the epoxy resin composite material.Described epoxy resin is bisphenol f type epoxy resin；Described curing agent is imidazoles
And acid anhydride type curing agent, the addition of acid anhydride type curing agent is the 85wt.% of epoxy resin, and the addition of imidazole curing agent is
The 1wt.% of epoxy resin.
The detailed process of wherein step (2) is as follows：
(2-1) disperses：The mixed fillers obtained in step (1) are added in epoxy resin, ultrasonic wave disperses or machine
Tool is stirred and causes uniform filling dispersion, obtains epoxy resin/filler dispersion system.Mechanical agitation speed is 800 rpms, is stirred
The time is mixed for 2 hours；Ultrasonic dispersing time is 1 hour.
After (2-2) is by the epoxy resin obtained by step (2-1)/filler dispersion system vacuum abjection bubble, curing agent is added,
And further high-speed stirred and abjection bubble, obtain modified epoxy dispersion.The high-speed stirred and abjection bubble mistake
Cheng Caiyong rotations/revolution mixer, high-speed stirred speed is 1600 rpms, and the rotating speed during abjection bubble is 2000 turns
It is per minute.
The modified epoxy dispersion that step (2-2) is obtained is carried out curing reaction by (2-3), that is, obtain the epoxy
Resin composite materials.
The solidification process includes low temperature precuring and hot setting；Precuring temperature is 60 DEG C, and pre-cure time is 2 small
When；Hot setting temperature is 150 DEG C, and high temperature pre-cure time is 5 hours.
Test analysis：
The test of thermal conductivity and shear viscosity is carried out to the epoxy resin composite material that embodiment 1-7 is provided, as a result such as
Shown in Fig. 1, Fig. 2, Fig. 3.
Suspension system is 100s in shear rate when shear viscosity is 30 DEG C-1Shear viscosity.
Obtained according to interpretation, when boron nitride loading reaches volume fraction 15%.Epoxy resin composite wood
The thermal conductivity factor of material reaches 1.01W/mK, and viscosity is 12.8Pas, when the loading of increase boron nitride is continued to 18%,
Viscosity is increased rapidly to 42.8Pas, and this is said when boron nitride loading is 12%, has reached the heat conduction excess effusion value of system,
Sufficient passage of heat is formd in system, addition boron nitride thermal conductivity factor has been further continued for and is not almost lifted, but viscosity
But rapid increase, at this moment adds Ball-type packing, while further reducing the viscosity of system, effectively raises compound system
Thermal conductivity.Confirm that the multiple dimensioned heat filling modified epoxy resin composite that the present invention is provided is that one kind has well processed
The Heat Conduction Material of performance, has application value very high, especially electronic package material field in efficient thermal interfacial material, for example for
Surface-mounted integrated circuit encapsulation etc..
As it will be easily appreciated by one skilled in the art that the foregoing is only presently preferred embodiments of the present invention, it is not used to
The limitation present invention, all any modification, equivalent and improvement made within the spirit and principles in the present invention etc., all should include
Within protection scope of the present invention.
Claims (9)
1. a kind of epoxy resin heat conduction composite, it is characterised in that be dispersed with volume ratio 5% to 20% in the epoxy
Inorganic filler, the inorganic filler include two-dimensional slice inorganic filler and spherical inorganic filler.
2. epoxy resin heat conduction composite as claimed in claim 1, it is characterised in that the two-dimensional slice inorganic filler it is flat
Between 10 microns to 40 microns, the average grain diameter of the spherical inorganic filler is between 5 microns to 40 microns for equal particle diameter.
3. epoxy resin heat conduction composite as claimed in claim 1, it is characterised in that the two-dimensional slice inorganic filler and institute
The volume ratio of spherical inorganic filler is stated 4:1 to 1:Between 1.
4. epoxy resin heat conduction composite as claimed in claim 1, it is characterised in that the inorganic filler is aluminum oxide, nitrogen
Change at least one in boron, aluminium nitride, magnesia, zinc oxide, silica.
5. epoxy resin heat conduction composite as claimed in claim 1, it is characterised in that the epoxy resin be bisphenol A-type or
Bisphenol f type epoxy resin.
6. epoxy resin heat conduction composite as claimed in claim 1, it is characterised in that the epoxy resin heat conduction composite
Thermal conductivity factor be not less than 0.91W/mK, at 30 DEG C its viscosity be less than 20Pas.
7. the method for preparing epoxy resin heat conduction composite as claimed in any one of claims 1 to 6, it is characterised in that bag
Include following steps：
(1) two-dimensional slice inorganic filler and spherical inorganic filler are pressed 4:1 to 1:1 volume ratio carries out dispensing, after fully drying
Uniform mixing, obtains mixed fillers；
(2) mixed fillers in step (1) are added in epoxy resin, dispersed, de-bubbled solidify afterwards, that is, obtain described
Epoxy resin heat conduction composite.
8. preparation method as claimed in claim 7, it is characterised in that in the step (2), it is described it is dispersed be using ultrasound
Dispersion and the method for high-speed stirred so that the mixed fillers are dispersed in epoxy resin-base material；Preferably, it is described
The rotating speed that high-speed stirred is used is not less than 1000 rpms.
9. epoxy resin heat conduction composite as claimed in any one of claims 1 to 6 as electronic package material application.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109913185A (en) * | 2019-03-11 | 2019-06-21 | 中国科学院合肥物质科学研究院 | A kind of multilayered structure heat-conductive composite material and preparation method thereof containing heat conducting film |
| CN110183824A (en) * | 2019-07-09 | 2019-08-30 | 南通德泰新材料科技有限公司 | A kind of heat conductive insulating epoxy resin lamination composite material and preparation method and application |
| CN112778703A (en) * | 2021-01-06 | 2021-05-11 | 沈阳航空航天大学 | High-toughness and heat-conducting epoxy resin composite material and preparation method thereof |
| CN113583388A (en) * | 2021-06-29 | 2021-11-02 | 福建师范大学泉港石化研究院 | Heat-conducting epoxy resin composite material and preparation method thereof |
| CN113698730A (en) * | 2021-08-23 | 2021-11-26 | 浙江华正新材料股份有限公司 | Resin composition, prepreg, circuit substrate and preparation method and application thereof |
| WO2022205582A1 (en) * | 2021-03-30 | 2022-10-06 | 太阳油墨（苏州）有限公司 | Thermosetting resin composition, cured product, and electronic component |
| CN116003967A (en) * | 2022-12-23 | 2023-04-25 | 国网智能电网研究院有限公司 | High-heat-conductivity epoxy composition, cured product, and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109913185A (en) * | 2019-03-11 | 2019-06-21 | 中国科学院合肥物质科学研究院 | A kind of multilayered structure heat-conductive composite material and preparation method thereof containing heat conducting film |
| CN110183824A (en) * | 2019-07-09 | 2019-08-30 | 南通德泰新材料科技有限公司 | A kind of heat conductive insulating epoxy resin lamination composite material and preparation method and application |
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| CN113583388A (en) * | 2021-06-29 | 2021-11-02 | 福建师范大学泉港石化研究院 | Heat-conducting epoxy resin composite material and preparation method thereof |
| CN113698730A (en) * | 2021-08-23 | 2021-11-26 | 浙江华正新材料股份有限公司 | Resin composition, prepreg, circuit substrate and preparation method and application thereof |
| CN116003967A (en) * | 2022-12-23 | 2023-04-25 | 国网智能电网研究院有限公司 | High-heat-conductivity epoxy composition, cured product, and preparation method and application thereof |
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