CN106751526B - A kind of thermally conductive composite material of epoxy resin and its preparation and application - Google Patents
A kind of thermally conductive composite material of epoxy resin and its preparation and application Download PDFInfo
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- CN106751526B CN106751526B CN201611244696.8A CN201611244696A CN106751526B CN 106751526 B CN106751526 B CN 106751526B CN 201611244696 A CN201611244696 A CN 201611244696A CN 106751526 B CN106751526 B CN 106751526B
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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
Abstract
The invention discloses a kind of thermally conductive composite material of epoxy resin and its preparation and application, wherein, the thermally conductive composite material of the epoxy resin 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 by improving heat filling structure and additive amount etc. crucial in the thermally conductive composite material of the epoxy resin, and use corresponding preparation method, it can effectively solve the problem that epoxy resin composite material heating conduction is bad compared with prior art, the problem of viscosity height etc., pass through the compound addition of the heat filling of variety classes and pattern, it is prepared and has both high-termal conductivity, low-viscosity epoxy resin base heat-conductive composite material, be particularly suitable for use as electronic package material.
Description
Technical field
The invention belongs to thermal interfacial material fields, more particularly, to a kind of thermally conductive composite material of epoxy resin and its system
It is standby with application.
Background technique
Nowadays the use of electronic product is becoming increasingly prevalent, while also developing towards the direction of micromation, answers
Used time can generate a large amount of heat, and the raising of electronic device temperature can all have service life, efficiency and energy consumption aspect very big
It influences, therefore improve heat-sinking capability to become the hot spot of research work.Heat conductive insulating encapsulating material with high heat dispersion is to mention
The key link of high electronic component job stability and service life.Plastic Package is with its excellent electrical insulation capability, processing
Performance and cost advantage are widely used in thermal interfacial material and Electronic Packaging field, and wherein epoxy resin is due to shrinking percentage
Low, the advantages that adhesive property is good, corrosion resistance and good, account for 90% of plastic encapsulant or more.However epoxy resin thermal conductivity
Can be poor, it causes electronic element radiating difficult, is easy aging, service life is short.
The inorganic filler (such as aluminium oxide, aluminium nitride, boron nitride, magnesia) that high heat conductance is added into epoxy resin can be with
The effective thermal conductivity for improving basis material.But it usually requires just significantly improve composite material thermal conductivity in very high loading
Rate.The high filler loading capacity of inorganic filler results in the mechanical property of composite material and processing performance declines to a great extent.Specifically, this will
Lead to the high viscosity of epoxy resin composite system, it is difficult to the encapsulation of electronic component be effectively performed.
In this background, studying a kind of epoxy resin-base composite material with low viscosity and high thermal conductivity characteristic just has weight
Big science and practical value.
Summary of the invention
Aiming at the above defects or improvement requirements of the prior art, the purpose of the present invention is to provide a kind of epoxy resin is thermally conductive
Composite material and its preparation and application, wherein by heat filling structure crucial in the thermally conductive composite material of the epoxy resin,
And additive amount etc. improves, and uses corresponding preparation method, can effectively solve the problem that epoxy resin compared with prior art
The problem of composite material heating conduction is bad, viscosity height etc. passes through the compound addition of the heat filling of variety classes and pattern, preparation
Have both the epoxy resin based thermal conductive composite of low viscosity and high thermal conductivity characteristic；It is inorganic in the thermally conductive composite material of the epoxy resin
Volume ratio of the filler additive amount down to 5% to 20%, and thermal coefficient 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 the good mechanical property of the composite material and processing performance preparation, it is especially suitable
For as electronic package material.
To achieve the above object, according to one aspect of the present invention, a kind of thermally conductive composite material of epoxy resin is provided,
It is characterized in that, be dispersed with the inorganic filler of volume ratio 5% to 20% in the epoxy, the inorganic filler includes two-dimensional slice
Layer inorganic filler and spherical inorganic filler.
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
In 4:1 between 1:1.
As present invention further optimization, the inorganic filler is aluminium oxide, boron nitride, aluminium nitride, magnesia, oxidation
At least one of zinc, silica.
As present invention further optimization, the epoxy resin is bisphenol A-type or bisphenol f type epoxy resin.
As present invention further optimization, the thermal coefficient of the thermally conductive composite material of epoxy resin 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 present invention provides the sides of the preparation such as hot composite material of above-mentioned epoxy resin derivative
Method, which comprises the following steps:
(1) two-dimensional slice inorganic filler and spherical inorganic filler are subjected to ingredient by the volume ratio of 4:1 to 1:1, it is sufficiently dry
Uniformly mixing, obtains mixed fillers after dry；
(2) mixed fillers in step (1) are added in epoxy resin, evenly dispersed, solidification is after de-bubbled to get arriving
The thermally conductive composite material of epoxy resin.
As present invention further optimization, in the step (2), it is described it is evenly 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 revolving speed of use is not less than 1000 rpms.
Another aspect according to the invention, the present invention provides the thermally conductive composite materials of above-mentioned epoxy resin as Electronic Packaging
The application of material.
In general, through the invention it is contemplated above technical scheme is compared with the prior art, can obtain down and show
Beneficial effect:
(1) two-dimensional slice inorganic filler provided by the invention and spherical inorganic filler modified epoxy resin composite, by
Compound system viscosity can be effectively reduced after Ball-type packing has better mobility, Ball-type packing to be added in the base, thus
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 is between 10 microns to 40 microns (that is, two-dimensional slice
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
Length and width an order of magnitude of slice plane is at least needed to be less than, such as can be 100nm to 800nm.
(2) two-dimensional slice inorganic filler provided by the invention and spherical inorganic filler modified epoxy resin composite, by
It is filled into epoxy resin after the filler of different-shape mixes in proper proportions, optimizes the dispersibility of system filler, from
And the viscosity of compound system is reduced, improve processing performance.
(3) two-dimensional slice inorganic filler provided by the invention and spherical inorganic filler modified epoxy resin composite, two
Dimension lamella inorganic filler mainly constructs passage of heat and forms heat conduction network, and the addition of Ball-type packing shows apparent association
Same effect improves the interaction between filler and epoxy resin-base, drops while the effective thermally conductive threshold of building seeps network
Low system viscosity realizes that heating conduction greatly improves.
(4) composite material and preparation method thereof provided by the invention, step is simple, and reaction condition is mild, is suitble to industry big
Large-scale production.
(5) two-dimensional slice inorganic filler provided by the invention and spherical inorganic filler modified epoxy resin composite, are answered
For thermal interfacial material, thermal conductivity can be reinforced, submit heat exchanger effectiveness.It is particularly suitable for electronic package material, such as collecting
At circuit board package etc., electronic element radiating performance can be greatly improved, electronic component is delayed under the premise of guaranteeing processing performance
Heat ageing simultaneously guarantees its job stability, to extend the service life of electronic product.
Preferred embodiment adjusts described multiple by adjusting the mixed proportion of two-dimensional slice inorganic filler and spherical inorganic filler
The processing performance and heating conduction of condensation material.
Preferred embodiment adjusts the condition of cure of the composite material by adjusting epoxy resin and curing agent type, thus
Meet the particular/special requirement of different construction sites.
Preferred embodiment, by selecting different types of epoxy resin, so that the composite material has different processabilities
Energy and physical and chemical performance, meet different industrial requirements.
Detailed description of the invention
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
Match the viscosity comparison diagram of obtained epoxy resin composite material；
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 obtained epoxy resin composite material；
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 obtained epoxy resin composite material 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 objectives, technical solutions, and advantages of the present invention clearer, with reference to the accompanying drawings and embodiments, right
The present invention is further elaborated.It should be appreciated that described herein, specific examples are only used to explain the present invention, not
For limiting the present invention.As long as in addition, technical characteristic involved in the various embodiments of the present invention described below that
Not constituting conflict between this can be combined with each other.
Epoxy resin composite material provided by the invention, it is evenly dispersed in the epoxy to have volume ratio 5% to 20%
Inorganic filler, the inorganic filler includes that (these inorganic fillers can be from for two-dimensional slice inorganic filler and spherical inorganic filler
Buy in the market), 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 is between 5 microns to 40 microns, the volume ratio of the two-dimensional slice inorganic filler and spherical inorganic filler
In 4:1 between 1:1.Preferably, the average grain diameter of the two-dimensional slice inorganic filler is at 30 microns to 40 microns, the spherical shape
The average grain diameter of inorganic filler is at 30 microns to 40 microns, the volume ratio of the two-dimensional slice inorganic filler and spherical inorganic filler
In 2:1 between 1:1.
The inorganic filler can be one of aluminium oxide, boron nitride, aluminium nitride, magnesia, zinc oxide, silica
Or two kinds, preferably one or both of aluminium oxide, boron nitride, aluminium nitride.
Epoxy resin composite material provided by the invention, heating conduction is tested according to testing standard ASTMC1113, thermally conductive
Coefficient is not less than 0.91W/mK, and viscosity is less than 20Pas at 30 DEG C.
The present invention mentions total epoxy resin composite material, can be according to general filler adding method according to formula rate
Preparation, preferably prepares by the following method:
(1) two-dimensional slice inorganic filler and the spherical inorganic filler of formula rate are taken, sufficiently uniformly mixes, obtains after drying
Mixed fillers.
(2) mixed fillers obtained in step (1) are added in epoxy resin, it is evenly dispersed, solidify after de-bubbled, i.e.,
Obtain the epoxy resin composite material.Preferably, the 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 additive amount of curing agent is 6~90wt.% of epoxy resin.
Wherein detailed process is as follows for step (2):
(2-1) dispersion: mixed fillers obtained in step (1) are added in epoxy resin, ultrasonic wave dispersion or machine
Tool stirs so that uniform filling dispersion, obtains epoxy resin/filler dispersion system.Preferably, the ultrasonic disperse power is preferred
Are as follows: 200 watts, temperature is 50 DEG C -70 DEG C, ultrasonic disperse 0.5-2 hours；The high-speed stirred are as follows: 40 DEG C -70 DEG C, 600-2000
Rev/min, it stirs 1-2 hours.
Curing agent is added by after the resulting epoxy resin of step (2-1)/filler dispersion system vacuum abjection bubble in (2-2),
And further high-speed stirred and abjection bubble, obtain modified epoxy dispersion.The high-speed stirred and abjection bubble mistake
Cheng Caiyong rotation/revolution blender, high-speed stirred speed are 1600~1900 rpms, and the revolving speed during abjection bubble is
2000~2100 rpms.
The modified epoxy dispersion that (2-3) obtains step (2-2) carries out curing reaction to get the epoxy is arrived
Resin composite materials.
The solidification process includes low temperature precuring and hot setting；Precuring temperature is 60 DEG C~100 DEG C, when 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.
Epoxy resin composite material provided by the invention has good machining while guaranteeing heating conduction
Performance, viscosity are tested according to testing standard Anton Paar MCR302, and 20Pas is less than at 30 DEG C, are suitable for electronic seal
Package material.
The following are specific embodiments:
Embodiment 1
A kind of epoxy resin composite material, the in the epoxy evenly dispersed inorganic filler for having 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, and described two
Dimension lamella inorganic filler is boron nitride.The epoxy resin composite material, heating conduction is according to testing standard ASTM C1113
Test, thermal coefficient 0.81W/mK, viscosity are 7.8Pas at 30 DEG C.
A kind of epoxy resin composite material is prepared by the following method according to formula rate:
(1) two-dimensional slice inorganic filler is taken, sufficiently the filler after drying.
(2) two-dimensional slice inorganic filler obtained in step (1) is added in epoxy resin, evenly dispersed, de-bubbled
After solidify to get to the epoxy resin composite material.The epoxy resin is bisphenol A type epoxy resin；The solidification
Agent is imidazoles and acid anhydride type curing agent, and the additive amount of acid anhydride type curing agent is the 85wt.% of epoxy resin, imidazole curing agent
Additive amount be epoxy resin 1wt.%.
Wherein detailed process is as follows for step (2):
(2-1) dispersion: filler obtained in step (1) is added in epoxy resin, and ultrasonic wave dispersion or machinery stir
It mixes so that uniform filling dispersion, obtains epoxy resin/filler dispersion system.Mechanical stirring speed is 800 rpms, when stirring
Between be 2 hours；Ultrasonic dispersing time is 1 hour.
Curing agent is added by after the resulting epoxy resin of step (2-1)/filler dispersion system vacuum abjection bubble in (2-2),
And further high-speed stirred and abjection bubble, obtain modified epoxy dispersion.The high-speed stirred and abjection bubble mistake
Cheng Caiyong rotation/revolution blender, high-speed stirred 3 minutes, speed was 1600 rpms, was deviate from bubble process 2 minutes, revolving speed
It is 2000 rpms.
The modified epoxy dispersion that (2-3) obtains step (2-2) carries out curing reaction to get the epoxy is arrived
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 evenly dispersed inorganic filler for having 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, and described two
Dimension lamella inorganic filler is boron nitride.The epoxy resin composite material, heating conduction is according to testing standard ASTM C1113
Test, thermal coefficient 1.01W/mK, viscosity are 12.8Pas at 30 DEG C.
A kind of epoxy resin composite material is prepared by the following method according to formula rate:
(1) two-dimensional slice inorganic filler is taken, sufficiently the filler after drying.
(2) two-dimensional slice inorganic filler obtained in step (1) is added in epoxy resin, evenly dispersed, de-bubbled
After solidify to get to the epoxy resin composite material.The epoxy resin is bisphenol A type epoxy resin；The solidification
Agent is imidazoles and acid anhydride type curing agent, and the additive amount of acid anhydride type curing agent is the 85wt.% of epoxy resin, imidazole curing agent
Additive amount be epoxy resin 1wt.%.
Wherein detailed process is as follows for step (2):
(2-1) dispersion: filler obtained in step (1) is added in epoxy resin, and ultrasonic wave dispersion or machinery stir
It mixes so that uniform filling dispersion, obtains epoxy resin/filler dispersion system.Mechanical stirring speed is 800 rpms, when stirring
Between be 2 hours；Ultrasonic dispersing time is 1 hour.
Curing agent is added by after the resulting epoxy resin of step (2-1)/filler dispersion system vacuum abjection bubble in (2-2),
And further high-speed stirred and abjection bubble, obtain modified epoxy dispersion.The high-speed stirred and abjection bubble mistake
Cheng Caiyong rotation/revolution blender, high-speed stirred 3 minutes, speed was 1600 rpms, was deviate from bubble process 2 minutes, revolving speed
It is 2000 rpms.
The modified epoxy dispersion that (2-3) obtains step (2-2) carries out curing reaction to get the epoxy is arrived
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 evenly dispersed inorganic filler for having 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, and described two
Dimension lamella inorganic filler is boron nitride.The epoxy resin composite material, heating conduction is according to testing standard ASTM C1113
Test, thermal coefficient 1.09W/mK, viscosity are 42.8Pas at 30 DEG C.
A kind of epoxy resin composite material is prepared by the following method according to formula rate:
(1) two-dimensional slice inorganic filler is taken, sufficiently the filler after drying.
(2) two-dimensional slice inorganic filler obtained in step (1) is added in epoxy resin, evenly dispersed, de-bubbled
After solidify to get to the epoxy resin composite material.The epoxy resin is bisphenol A type epoxy resin；The solidification
Agent is imidazoles and acid anhydride type curing agent, and the additive amount of acid anhydride type curing agent is the 85wt.% of epoxy resin, imidazole curing agent
Additive amount be epoxy resin 1wt.%.
Wherein detailed process is as follows for step (2):
(2-1) dispersion: filler obtained in step (1) is added in epoxy resin, and ultrasonic wave dispersion or machinery stir
It mixes so that uniform filling dispersion, obtains epoxy resin/filler dispersion system.Mechanical stirring speed is 800 rpms, when stirring
Between be 2 hours；Ultrasonic dispersing time is 1 hour.
Curing agent is added by after the resulting epoxy resin of step (2-1)/filler dispersion system vacuum abjection bubble in (2-2),
And further high-speed stirred and abjection bubble, obtain modified epoxy dispersion.The high-speed stirred and abjection bubble mistake
Cheng Caiyong rotation/revolution blender, high-speed stirred 3 minutes, speed was 1600 rpms, was deviate from bubble process 2 minutes, revolving speed
It is 2000 rpms.
The modified epoxy dispersion that (2-3) obtains step (2-2) carries out curing reaction to get the epoxy is arrived
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 evenly dispersed inorganic filler for having 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 aluminium oxide.
The epoxy resin composite material, heating conduction are tested according to testing standard ASTM C1113, and thermal coefficient is
0.91W/mK, viscosity are tested according to testing standard Anton Paar MCR302, are 8.9Pas at 30 DEG C.
A kind of epoxy resin composite material is prepared by the following method according to formula rate:
(1) two-dimensional slice inorganic filler and the spherical inorganic filler of formula rate are taken, sufficiently uniformly mixes, obtains after drying
Mixed fillers.
(2) mixed fillers obtained in step (1) are added in epoxy resin, it is evenly dispersed, solidify after de-bubbled, i.e.,
Obtain the epoxy resin composite material.The epoxy resin is bisphenol A type epoxy resin；The curing agent is imidazoles
And acid anhydride type curing agent, the additive amount of acid anhydride type curing agent are the 85wt.% of epoxy resin, the additive amount of imidazole curing agent is
The 1wt.% of epoxy resin.
Wherein detailed process is as follows for step (2):
(2-1) dispersion: mixed fillers obtained in step (1) are added in epoxy resin, ultrasonic wave dispersion or machine
Tool stirs so that uniform filling dispersion, obtains epoxy resin/filler dispersion system.Mechanical stirring speed is 800 rpms, is stirred
Mixing the time is 2 hours；Ultrasonic dispersing time is 1 hour.
Curing agent is added by after the resulting epoxy resin of step (2-1)/filler dispersion system vacuum abjection bubble in (2-2),
And further high-speed stirred and abjection bubble, obtain modified epoxy dispersion.The high-speed stirred and abjection bubble mistake
Cheng Caiyong rotation/revolution blender, high-speed stirred speed are 1600 rpms, and the revolving speed during abjection bubble is 2000 turns
Per minute.
The modified epoxy dispersion that (2-3) obtains step (2-2) carries out curing reaction to get the epoxy is arrived
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 evenly dispersed inorganic filler for having 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 aluminium oxide.
The epoxy resin composite material, heating conduction are tested according to testing standard ASTM C1113, and thermal coefficient is
1.06W/mK, viscosity are tested according to testing standard Anton Paar MCR302, are 11.2Pas at 30 DEG C.
A kind of epoxy resin composite material is prepared by the following method according to formula rate:
(1) two-dimensional slice inorganic filler and the spherical inorganic filler of formula rate are taken, sufficiently uniformly mixes, obtains after drying
Mixed fillers.
(2) mixed fillers obtained in step (1) are added in epoxy resin, it is evenly dispersed, solidify after de-bubbled, i.e.,
Obtain the epoxy resin composite material.The epoxy resin is bisphenol A type epoxy resin；The curing agent is imidazoles
And acid anhydride type curing agent, the additive amount of acid anhydride type curing agent are the 85wt.% of epoxy resin, the additive amount of imidazole curing agent is
The 1wt.% of epoxy resin.
Wherein detailed process is as follows for step (2):
(2-1) dispersion: mixed fillers obtained in step (1) are added in epoxy resin, ultrasonic wave dispersion or machine
Tool stirs so that uniform filling dispersion, obtains epoxy resin/filler dispersion system.Mechanical stirring speed is 800 rpms, is stirred
Mixing the time is 2 hours；Ultrasonic dispersing time is 1 hour.
Curing agent is added by after the resulting epoxy resin of step (2-1)/filler dispersion system vacuum abjection bubble in (2-2),
And further high-speed stirred and abjection bubble, obtain modified epoxy dispersion.The high-speed stirred and abjection bubble mistake
Cheng Caiyong rotation/revolution blender, high-speed stirred speed are 1600 rpms, and the revolving speed during abjection bubble is 2000 turns
Per minute.
The modified epoxy dispersion that (2-3) obtains step (2-2) carries out curing reaction to get the epoxy is arrived
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 evenly dispersed inorganic filler for having 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 aluminium oxide.
The epoxy resin composite material, heating conduction are tested according to testing standard ASTM C1113, and thermal coefficient is
1.16W/mK, viscosity are tested according to testing standard Anton Paar MCR302, are 12.2Pas at 30 DEG C.
A kind of epoxy resin composite material is prepared by the following method according to formula rate:
(1) two-dimensional slice inorganic filler and the spherical inorganic filler of formula rate are taken, sufficiently uniformly mixes, obtains after drying
Mixed fillers.
(2) mixed fillers obtained in step (1) are added in epoxy resin, it is evenly dispersed, solidify after de-bubbled, i.e.,
Obtain the epoxy resin composite material.The epoxy resin is bisphenol A type epoxy resin；The curing agent is imidazoles
And acid anhydride type curing agent, the additive amount of acid anhydride type curing agent are the 85wt.% of epoxy resin, the additive amount of imidazole curing agent is
The 1wt.% of epoxy resin.
Wherein detailed process is as follows for step (2):
(2-1) dispersion: mixed fillers obtained in step (1) are added in epoxy resin, ultrasonic wave dispersion or machine
Tool stirs so that uniform filling dispersion, obtains epoxy resin/filler dispersion system.Mechanical stirring speed is 800 rpms, is stirred
Mixing the time is 2 hours；Ultrasonic dispersing time is 1 hour.
Curing agent is added by after the resulting epoxy resin of step (2-1)/filler dispersion system vacuum abjection bubble in (2-2),
And further high-speed stirred and abjection bubble, obtain modified epoxy dispersion.The high-speed stirred and abjection bubble mistake
Cheng Caiyong rotation/revolution blender, high-speed stirred speed are 1600 rpms, and the revolving speed during abjection bubble is 2000 turns
Per minute.
The modified epoxy dispersion that (2-3) obtains step (2-2) carries out curing reaction to get the epoxy is arrived
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 evenly dispersed inorganic filler for having 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 aluminium oxide.
The epoxy resin composite material, heating conduction are tested according to testing standard ASTM C1113, and thermal coefficient is
1.26W/mK, viscosity are tested according to testing standard Anton Paar MCR302, are 16.2Pas at 30 DEG C.
A kind of epoxy resin composite material is prepared by the following method according to formula rate:
(1) two-dimensional slice inorganic filler and the spherical inorganic filler of formula rate are taken, sufficiently uniformly mixes, obtains after drying
Mixed fillers.
(2) mixed fillers obtained in step (1) are added in epoxy resin, it is evenly dispersed, solidify after de-bubbled, i.e.,
Obtain the epoxy resin composite material.The epoxy resin is bisphenol A type epoxy resin；The curing agent is imidazoles
And acid anhydride type curing agent, the additive amount of acid anhydride type curing agent are the 85wt.% of epoxy resin, the additive amount of imidazole curing agent is
The 1wt.% of epoxy resin.
Wherein detailed process is as follows for step (2):
(2-1) dispersion: mixed fillers obtained in step (1) are added in epoxy resin, ultrasonic wave dispersion or machine
Tool stirs so that uniform filling dispersion, obtains epoxy resin/filler dispersion system.Mechanical stirring speed is 800 rpms, is stirred
Mixing the time is 2 hours；Ultrasonic dispersing time is 1 hour.
Curing agent is added by after the resulting epoxy resin of step (2-1)/filler dispersion system vacuum abjection bubble in (2-2),
And further high-speed stirred and abjection bubble, obtain modified epoxy dispersion.The high-speed stirred and abjection bubble mistake
Cheng Caiyong rotation/revolution blender, high-speed stirred speed are 1600 rpms, and the revolving speed during abjection bubble is 2000 turns
Per minute.
The modified epoxy dispersion that (2-3) obtains step (2-2) carries out curing reaction to get the epoxy is arrived
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 evenly dispersed inorganic filler for having 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 aluminium oxide.
The epoxy resin composite material, heating conduction are tested according to testing standard ASTM C1113, and thermal coefficient is
1.26W/mK, viscosity are tested according to testing standard Anton Paar MCR302, are 16.2Pas at 30 DEG C.
A kind of epoxy resin composite material is prepared by the following method according to formula rate:
(1) two-dimensional slice inorganic filler and the spherical inorganic filler of formula rate are taken, sufficiently uniformly mixes, obtains after drying
Mixed fillers.
(2) mixed fillers obtained in step (1) are added in epoxy resin, it is evenly dispersed, solidify after de-bubbled, i.e.,
Obtain the epoxy resin composite material.The epoxy resin is bisphenol f type epoxy resin；The curing agent is imidazoles
And acid anhydride type curing agent, the additive amount of acid anhydride type curing agent are the 85wt.% of epoxy resin, the additive amount of imidazole curing agent is
The 1wt.% of epoxy resin.
Wherein detailed process is as follows for step (2):
(2-1) dispersion: mixed fillers obtained in step (1) are added in epoxy resin, ultrasonic wave dispersion or machine
Tool stirs so that uniform filling dispersion, obtains epoxy resin/filler dispersion system.Mechanical stirring speed is 800 rpms, is stirred
Mixing the time is 2 hours；Ultrasonic dispersing time is 1 hour.
Curing agent is added by after the resulting epoxy resin of step (2-1)/filler dispersion system vacuum abjection bubble in (2-2),
And further high-speed stirred and abjection bubble, obtain modified epoxy dispersion.The high-speed stirred and abjection bubble mistake
Cheng Caiyong rotation/revolution blender, high-speed stirred speed are 1600 rpms, and the revolving speed during abjection bubble is 2000 turns
Per minute.
The modified epoxy dispersion that (2-3) obtains step (2-2) carries out curing reaction to get the epoxy is arrived
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 embodiment 1-7 epoxy resin composite material 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.
It is obtained according to analysis of experimental results, when boron nitride loading reaches volume fraction 15%.Epoxy resin composite wood
The thermal coefficient of material reaches 1.01W/mK, viscosity 12.8Pas, when continuing to increase the loading of boron nitride to 18%,
Viscosity is increased rapidly to 42.8Pas, this says when boron nitride loading is 12%, has reached the thermally conductive excess effusion value of system,
Sufficient passage of heat has been formd in system, is further continued for addition boron nitride thermal coefficient almost without promotion, but viscosity
But at this moment Ball-type packing is added in rapid increase, while further reducing the viscosity of system, effectively raise compound system
Thermal conductivity.Confirm that multiple dimensioned heat filling modified epoxy resin composite provided by the invention is a kind of with well processed
The Heat Conduction Material of performance has a very high application value, especially electronic package material field in efficient thermal interfacial material, such as
Integrated circuit board encapsulation etc..
As it will be easily appreciated by one skilled in the art that the foregoing is merely illustrative of the preferred embodiments of the present invention, not to
The limitation present invention, any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should all include
Within protection scope of the present invention.
Claims (7)
1. a kind of thermally conductive composite material of epoxy resin, which is characterized in that be dispersed with volume ratio 5% to 20% in the epoxy
Inorganic filler, the inorganic filler includes two-dimensional slice inorganic filler and spherical inorganic filler；The two-dimensional slice is inorganic to be filled out
The volume ratio of material and the spherical inorganic filler is in 4:1 between 1:1；The thermal coefficient of the thermally conductive composite material of epoxy resin
Not less than 0.91W/mK, its viscosity is less than 20Pas at 30 DEG C.
2. the thermally conductive composite material of epoxy resin as described in claim 1, which is characterized in that the two-dimensional slice inorganic filler is put down
Equal partial size is between 10 microns to 40 microns, and the average grain diameter of the spherical inorganic filler is between 5 microns to 40 microns.
3. the thermally conductive composite material of epoxy resin as described in claim 1, which is characterized in that the inorganic filler is aluminium oxide, nitrogen
Change at least one of boron, aluminium nitride, magnesia, zinc oxide, silica.
4. the thermally conductive composite material of epoxy resin as described in claim 1, which is characterized in that the epoxy resin be bisphenol A-type or
Bisphenol f type epoxy resin.
5. the method for preparing the thermally conductive composite material of epoxy resin as described in claim 1-4 any one, which is characterized in that packet
Include following steps:
(1) two-dimensional slice inorganic filler and spherical inorganic filler are subjected to ingredient by the volume ratio of 4:1 to 1:1, sufficiently after drying
Uniformly mixing, obtains mixed fillers；
(2) mixed fillers in step (1) are added in epoxy resin, it is evenly dispersed, solidify after de-bubbled to get described in
The thermally conductive composite material of epoxy resin.
6. preparation method as claimed in claim 5, which is characterized in that in the step (2), it is described it is evenly dispersed be using ultrasound
The method of dispersion and high-speed stirred, so that the mixed fillers are dispersed in epoxy resin-base material；The high-speed stirring
Revolving speed used by mixing is not less than 1000 rpms.
7. application of the thermally conductive composite material of epoxy resin as electronic package material as described in claim 1-4 any one.
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| 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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