CN112250996A - Micro-nano epoxy resin electronic packaging material and preparation method and application thereof - Google Patents
Micro-nano epoxy resin electronic packaging material and preparation method and application thereof Download PDFInfo
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- CN112250996A CN112250996A CN202011114362.5A CN202011114362A CN112250996A CN 112250996 A CN112250996 A CN 112250996A CN 202011114362 A CN202011114362 A CN 202011114362A CN 112250996 A CN112250996 A CN 112250996A
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- 239000002245 particle Substances 0.000 claims description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 claims description 9
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- 239000011231 conductive filler Substances 0.000 claims description 8
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- 229910052582 BN Inorganic materials 0.000 claims description 6
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
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- MWSKJDNQKGCKPA-UHFFFAOYSA-N 6-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1CC(C)=CC2C(=O)OC(=O)C12 MWSKJDNQKGCKPA-UHFFFAOYSA-N 0.000 claims description 5
- 239000004952 Polyamide Substances 0.000 claims description 5
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 claims description 5
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 claims description 5
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 claims description 5
- VYKXQOYUCMREIS-UHFFFAOYSA-N methylhexahydrophthalic anhydride Chemical compound C1CCCC2C(=O)OC(=O)C21C VYKXQOYUCMREIS-UHFFFAOYSA-N 0.000 claims description 5
- 229920002647 polyamide Polymers 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims 1
- 238000012545 processing Methods 0.000 abstract description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 30
- 239000002131 composite material Substances 0.000 description 25
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- 230000000052 comparative effect Effects 0.000 description 15
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 14
- 238000002156 mixing Methods 0.000 description 14
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- 229910021389 graphene Inorganic materials 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
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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
- C08K7/16—Solid spheres
- C08K7/18—Solid spheres inorganic
-
- 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
- C08K7/06—Elements
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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
- C08K7/10—Silicon-containing compounds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/08—Materials not undergoing a change of physical state when used
- C09K5/14—Solid materials, e.g. powdery or granular
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
- H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
- H01L23/293—Organic, e.g. plastic
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
- H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
- H01L23/293—Organic, e.g. plastic
- H01L23/295—Organic, e.g. plastic containing a filler
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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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- 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
- C08K2201/011—Nanostructured additives
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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
- C08K2201/016—Additives defined by their aspect ratio
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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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- Medicinal Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- General Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Computer Hardware Design (AREA)
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- Epoxy Resins (AREA)
Abstract
The invention belongs to the technical field of electronic packaging materials, and particularly relates to a micro-nano epoxy resin electronic packaging material and a preparation method and application thereof. The micro-nano epoxy resin electronic packaging material comprises 25-60 parts by volume of micron spherical heat-conducting filler, 0.5-5 parts by volume of nano one-dimensional heat-conducting filler and 30-75 parts by volume of epoxy resin. The invention takes the micron spherical heat-conducting filler as the main filler and the nanometer one-dimensional heat-conducting filler as the auxiliary filler, improves the heat-conducting property of the electronic packaging material, maintains the low viscosity of the packaging material and meets the processing requirement of the electronic packaging process.
Description
Technical Field
The invention belongs to the technical field of electronic packaging materials, and particularly relates to a micro-nano epoxy resin electronic packaging material and a preparation method and application thereof.
Background
With the development of 5G technology and the rapid update of portable mobile electronic devices, semiconductor chips are developed in the direction of higher integration, smaller size, larger storage capacity, and faster operation speed. The high-power semiconductor chip can generate a large amount of heat during working, and the development of effective heat management means and the preparation of high-heat-conductivity packaging materials are the keys for ensuring the working stability and safety of electronic equipment.
The plastic package using thermosetting epoxy resin as matrix has the characteristics of good insulation, light weight, easy mass production, low cost and the like, and accounts for more than 90 percent of the package of integrated circuits and electronic components at present. Epoxy resin is a poor thermal conductor (0.2W/m.K), and how to obtain an epoxy resin-based electronic packaging material with high thermal conductivity and electrical insulation becomes a research hotspot.
The filled heat-conducting high polymer material can be prepared by adding the inorganic filler with high heat conductivity coefficient into the epoxy resin matrix, has the advantages of low cost, simple processing technology, large-scale production and the like, and the heat-conducting property of the composite material can be adjusted by changing the factors such as the type, the size, the filling amount, the dispersion state, the interface interaction and the like of the filler. For micron thermally conductive fillers, it is generally desirable to form a complete thermally conductive network at high loading (70 vol.%), but this also results in a deterioration of the composite's process flow and mechanical properties.
At present, zero-dimensional spherical fillers are added into epoxy resin to help to reduce the viscosity of the composite material, but the defects are that point-to-point contact is adopted among the fillers, the contact area among the fillers is small, the capability of constructing a continuous effective heat conduction network is weak, and the heat conduction enhancement efficiency of the fillers in unit volume is lower than that of one-dimensional and two-dimensional heat conduction fillers. The nanometer heat-conducting filler, especially the two-dimensional nanometer filler (such as graphene and boron nitride nanosheets), has the advantage that a heat-conducting passage can be constructed with low filling amount, but the high surface energy of the nanometer heat-conducting filler causes the problems of easy agglomeration in epoxy resin, large interface thermal resistance between the filler and the epoxy resin, remarkably increased viscosity and the like. Therefore, there is an urgent need to design and prepare a high-performance epoxy resin electronic packaging material having high thermal conductivity and low viscosity.
Disclosure of Invention
In view of the above, the present invention provides a micro-nano epoxy resin electronic packaging material, in which a micro-spherical heat conductive filler and a nano one-dimensional heat conductive filler are used as fillers of the packaging material, so that the heat conductive performance of the electronic packaging material is improved, the low viscosity of the packaging material is maintained, and the processing requirements of the electronic packaging process are met.
In order to achieve the above purpose, the invention provides the following technical scheme:
the invention provides a micro-nano epoxy resin electronic packaging material which is prepared from the following raw materials in parts by volume: 25-60 parts of micron spherical heat-conducting filler, 0.5-5 parts of nano one-dimensional heat-conducting filler and 30-75 parts of epoxy resin.
Preferably, the micron spherical heat conducting filler is one or more of spherical alumina, spherical aluminum nitride and spherical boron nitride; the nano one-dimensional heat-conducting filler is one or two of silver nanowires and silicon carbide nanowires.
Preferably, the length-diameter ratio of the nanometer one-dimensional heat conduction filler is more than or equal to 80.
Preferably, the median particle size of the micron spherical heat-conducting filler is 1-120 μm.
Preferably, the epoxy resin comprises one or a mixture of any of bisphenol A epoxy resin, bisphenol F epoxy resin and novolac epoxy resin.
The invention also provides a preparation method of the micro-nano epoxy resin electronic packaging material, which comprises the following steps:
(1) dispersing the nanometer one-dimensional heat-conducting filler in an organic solvent to obtain nanometer one-dimensional heat-conducting filler dispersion liquid;
(2) dispersing the micron spherical heat-conducting filler and the epoxy resin in the nano one-dimensional heat-conducting filler dispersion liquid, and then removing the organic solvent through reduced pressure distillation to obtain a solvent-free dispersion system;
(3) and curing and molding the solvent-free dispersion system to obtain the micro-nano epoxy resin electronic packaging material.
Preferably, the organic solvent in step (1) includes one or more of methanol, ethanol, acetone, tetrahydrofuran, toluene and N, N' -dimethylformamide.
Preferably, the curing agent for curing molding includes one or more of 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, methylhexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, pyromellitic anhydride, triethylenetetramine, m-xylylenediamine, diaminodiphenylmethane, and polyamide curing agent.
Preferably, the curing and forming in the step (3) comprises pre-curing and post-curing in sequence, wherein the pre-curing temperature is 25-120 ℃, and the time is 0.5-5 hours; the post-curing temperature is 70-180 ℃, and the time is 2-8 hours.
The invention also provides the application of the micro-nano epoxy resin electronic packaging material in the technical scheme in electronic packaging.
The invention provides a micro-nano epoxy resin electronic packaging material which is prepared from the following raw materials in parts by volume: 25-60 parts of micron spherical heat-conducting filler, 0.5-5 parts of nano one-dimensional heat-conducting filler and 30-75 parts of epoxy resin. The invention takes the micron spherical heat-conducting filler as the main filler, and utilizes the characteristics of smooth surface and regular shape to reduce the friction and flow resistance between the filler and between the filler and the matrix in the shearing process, so that the micron spherical heat-conducting filler still has good flow property under high filling amount; the nanometer one-dimensional heat-conducting filler is used as an auxiliary filler, the nanometer one-dimensional heat-conducting filler with higher length-diameter ratio is limited and distributed in the unfilled area of the micrometer spherical heat-conducting filler to form a micro-nanometer heat-conducting filler network, so that the interface thermal resistance of the packaging material is reduced, meanwhile, the introduction of a small amount of the nanometer one-dimensional heat-conducting filler reduces the non-Newtonian index of the packaging material, is beneficial to the regulation and control of the flow performance of the packaging material, maintains the low viscosity of the packaging material while improving the heat-conducting performance, and meets the processing requirement of an.
In addition, compared with a single micron epoxy resin electronic packaging material, the micro-nano epoxy resin electronic packaging material provided by the invention has a lower thermal expansion coefficient and higher bending strength, and is beneficial to improving the thermal management efficiency, the working stability and the safety of an electronic device.
Drawings
Fig. 1 is a scanning electron microscope picture of silver nanowires used in example 1;
FIG. 2 is a scanning electron microscope picture of the micro-nano epoxy resin electronic packaging material in example 1;
FIG. 3 is a graph showing the relationship between apparent viscosity and shear rate at 25 ℃ of the composite materials obtained in example 1 and comparative example 1, and comparative example 2 and comparative example 3.
Detailed Description
The invention provides a micro-nano epoxy resin electronic packaging material which is prepared from the following raw materials in parts by volume: 25-60 parts of micron spherical heat-conducting filler, 0.5-5 parts of nano one-dimensional heat-conducting filler and 30-75 parts of epoxy resin.
In the present invention, as the raw material, commercially available products known to those skilled in the art may be used unless otherwise specified.
The micro-nano epoxy resin electronic packaging material provided by the invention comprises, by volume, 25-60 parts of micron spherical heat-conducting filler, preferably 27-58 parts, and more preferably 25-55 parts. In the present invention, the micron spherical heat conductive filler is preferably one or more of spherical alumina, spherical aluminum nitride and spherical boron nitride, and is further preferably spherical alumina. In the invention, the median particle diameter of the micron spherical heat-conducting filler is preferably 1-120 μm, more preferably 2-118 μm, and even more preferably 4-115 μm. The invention takes the micron spherical heat-conducting filler as the main filler, and utilizes the characteristics of smooth surface and regular shape to reduce the friction and flow resistance between the filler and between the filler and the matrix in the shearing process, so that the micron spherical heat-conducting filler still has good flow property under high filling amount.
Based on the volume parts of the micron spherical heat-conducting filler, the micro-nano epoxy resin electronic packaging material provided by the invention comprises 0.5-5 parts of the nano one-dimensional heat-conducting filler, preferably 0.6-4.8 parts, and more preferably 0.7-4.6 parts. In the invention, the nano one-dimensional heat-conducting filler is preferably one or two of silver nanowires and silicon carbide nanowires.
In the invention, the length-diameter ratio of the nano one-dimensional heat-conducting filler is preferably greater than or equal to 80, more preferably 80-250, and even more preferably 100-230. The diameter of the nanometer one-dimensional heat conduction filler is 50-100 nm, more preferably 52-98 nm, and even more preferably 55-95 nm. According to the invention, the nanometer one-dimensional heat-conducting filler is used as an auxiliary filler, and the nanometer one-dimensional heat-conducting filler with higher length-diameter ratio is limitedly distributed in the unfilled region of the micron spherical heat-conducting filler to construct a complete micro-nano filler network structure, so that on one hand, a good heat-conducting passage can be constructed, the defect of small contact area of the single micron spherical heat-conducting filler is overcome, and the heat-conducting property is improved; on the other hand, the processing fluidity advantage of the micron spherical heat-conducting filler filled epoxy resin composite material is not destroyed, and the low viscosity of the composite material is maintained.
Based on the volume parts of the micron spherical heat-conducting filler, the micro-nano epoxy resin electronic packaging material provided by the invention comprises 30-75 parts of epoxy resin, preferably 31-74 parts, and more preferably 32-72 parts. In the present invention, the epoxy resin preferably includes one or a mixture of any of bisphenol a type epoxy resin, bisphenol F type epoxy resin and novolac epoxy resin. The invention adopts the epoxy resin with a specific type, and can further reduce the viscosity of the composite material by utilizing the low viscosity characteristic of the epoxy resin.
The invention also provides a preparation method of the micro-nano epoxy resin electronic packaging material in the technical scheme, which comprises the following steps:
(1) dispersing the nanometer one-dimensional heat-conducting filler in an organic solvent to obtain nanometer one-dimensional heat-conducting filler dispersion liquid;
(2) dispersing the micron spherical heat-conducting filler and the epoxy resin in the nano one-dimensional heat-conducting filler dispersion liquid, and then removing the organic solvent through reduced pressure distillation to obtain a solvent-free dispersion system;
(3) and curing and molding the solvent-free dispersion system to obtain the micro-nano epoxy resin electronic packaging material.
The invention disperses the nanometer one-dimensional heat conduction filler in the organic solvent to obtain the nanometer one-dimensional heat conduction filler dispersion. In the present invention, the manner of dispersion is preferably carried out under ultrasonic conditions; the invention has no special requirements on the specific implementation parameters of the ultrasound, and can uniformly disperse the nano one-dimensional heat-conducting filler in the organic solvent. In the present invention, the organic solvent preferably includes one or more of methanol, ethanol, acetone, tetrahydrofuran, toluene, and N, N '-dimethylformamide, and more preferably tetrahydrofuran and N, N' -dimethylformamide. In the present invention, the concentration of the dispersion of the nano one-dimensional thermally conductive filler is preferably 1g/50mL to 1g/1000mL, more preferably 1g/70mL to 1g/980mL, and still more preferably 1g/80mL to 1g/950 mL.
After the nano one-dimensional heat-conducting filler dispersion liquid is obtained, the micron spherical heat-conducting filler and the epoxy resin are dispersed in the nano one-dimensional heat-conducting filler dispersion liquid, and the organic solvent is removed through reduced pressure distillation, so that a solvent-free dispersion system is obtained. In the invention, the micron spherical heat-conducting filler and the epoxy resin are preferably added into the nano one-dimensional heat-conducting filler dispersion liquid under the ultrasonic condition and/or the stirring condition to realize dispersion. The invention has no special requirements on the specific implementation parameters of the ultrasonic and/or stirring, and can obtain a uniform dispersion system. After uniform dispersion, the invention adopts a reduced pressure distillation mode to remove the organic solvent, and a solvent-free dispersion system is obtained. In the invention, the reduced pressure distillation is preferably carried out by adopting a circulating water vacuum pump, and the temperature of the reduced pressure distillation is preferably 25-100 ℃, and is further preferably 27-98 ℃. At the above temperature, the solvent in the system can be kept completely removed to obtain a solvent-free dispersion system.
After the solvent-free dispersion system is obtained, the solvent-free dispersion system is cured and molded to obtain the micro-nano epoxy resin electronic packaging material. In the invention, the curing agent is preferably added into the solvent-free dispersion system for curing and forming; the curing agent is preferably one or more of 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, methylhexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, pyromellitic anhydride, triethylenetetramine, m-xylylenediamine, diaminodiphenylmethane and polyamide curing agent. The mass ratio of the curing agent to the epoxy resin is preferably 1-88: 100, more preferably 3 to 85: 100, more preferably 5 to 83: 100.
after the addition of the curing agent, the present invention preferably employs a planetary centrifugal mixer for mixing. The invention has no special requirements on the concrete implementation parameters of the stirring, and can obtain a uniform mixing system. After the uniform mixing system is obtained, before the curing and forming, the solvent-free dispersion system is preferably subjected to vacuum de-bubbling treatment, the vacuum de-bubbling treatment is preferably performed by using a vacuum oil pump, the temperature of the vacuum de-bubbling treatment is 25-60 ℃, the preferred temperature is 27-58 ℃, the time of single vacuum de-bubbling treatment is 10-20 minutes, the preferred time is 15 minutes, and the times of the vacuum de-bubbling treatment are 2-4 times, and the preferred time is 3 times. According to the invention, through vacuum de-bubbling treatment, bubbles in the sample can be discharged, so that the subsequent curing reaction is facilitated.
In the invention, the curing molding comprises pre-curing and post-curing which are sequentially carried out, wherein the pre-curing temperature is preferably 25-120 ℃, further preferably 26-118 ℃, further preferably 28-115 ℃, and the time is preferably 0.5-5 h, further preferably 0.6-4.8 h, further preferably 0.8-4.5 h; the post-curing temperature is preferably 70-180 ℃, more preferably 75-175 ℃, more preferably 80-170 ℃, and the time is preferably 2-8 hours, more preferably 2.5-7.5 hours, more preferably 3-7 hours.
The invention also provides the application of the micro-nano epoxy resin electronic packaging material in the technical scheme or the micro-nano epoxy resin electronic packaging material prepared by the preparation method in the technical scheme in electronic packaging, and the application can meet the occasions with requirements on the viscosity performance of the packaging material.
For further illustration of the present invention, the micro-nano epoxy resin electronic packaging material provided by the present invention, the preparation method and the application thereof are described in detail below with reference to the accompanying drawings and examples, but they should not be construed as limiting the scope of the present invention.
Example 1
Preparing materials according to parts by volume: 40 parts of micron spherical alumina, 0.5 part of silver nanowires and 59.5 parts of bisphenol F epoxy resin, wherein the aspect ratio of the silver nanowires is about 125, the diameter of the silver nanowires is 80nm, and the median particle size of the micron spherical alumina is 5 mu m.
(1) Carrying out ultrasonic dispersion on silver nanowires and ethanol to form silver nanowire dispersion liquid, wherein the concentration of the dispersion liquid is 1g/50 mL;
(2) adding micron spherical alumina and bisphenol F epoxy resin into the silver nanowire dispersion liquid, performing ultrasonic dispersion to form a uniform dispersion system, and then performing reduced pressure distillation at 40 ℃ to remove ethanol to obtain a solvent-free dispersion system;
(3) adding 2-ethyl-4-methylimidazole (the mass ratio of 2-ethyl-4-methylimidazole to bisphenol F epoxy resin is 6: 100) into the solvent-free dispersion system, uniformly mixing by using a planetary centrifugal stirrer, performing vacuum de-bubbling treatment (15 minutes each time, repeating for 3 times) at 25 ℃, pre-curing for 2 hours at 60 ℃, and post-curing for 8 hours at 150 ℃ to obtain the micro-nano epoxy resin electronic packaging material.
FIG. 1 is a scanning electron micrograph of the silver nanowires of example 1, from which it can be seen that the average aspect ratio of the silver nanowires is 125 or more; fig. 2 is a scanning electron microscope image of a cross section of the micro-nano epoxy resin electronic packaging material obtained in example 1, and it can be seen from the image that silver nanowires are dispersed among spherical alumina to form a more continuous filler network.
Example 2
Preparing materials according to parts by volume: 50 parts of micron spherical alumina, 1 part of silicon carbide nanowires and 49 parts of bisphenol F type epoxy resin, wherein the length-diameter ratio of the silicon carbide nanowires is about 80, the diameter of the silicon carbide nanowires is 50nm, and the median particle size of the micron spherical alumina is 30 microns.
(1) Ultrasonically dispersing silicon carbide nanowires and methanol to form a silicon carbide nanowire dispersion liquid, wherein the concentration of the dispersion liquid is 1g/200 mL;
(2) adding micron spherical alumina and bisphenol F epoxy resin into the silicon carbide nanowire dispersion liquid, performing ultrasonic dispersion to form a uniform dispersion system, and then performing reduced pressure distillation at 25 ℃ to remove methanol to obtain a solvent-free dispersion system;
(3) adding 2-ethyl-4-methylimidazole (the mass ratio of 2-ethyl-4-methylimidazole to bisphenol F epoxy resin is 6: 100) into the solvent-free dispersion system, uniformly mixing by using a planetary centrifugal stirrer, performing vacuum de-bubbling treatment (15 minutes and 3 times) at 25 ℃, pre-curing for 2 hours at 60 ℃, and post-curing for 8 hours at 150 ℃ to obtain the micro-nano epoxy resin electronic packaging material.
Example 3
Preparing materials according to parts by volume: 25 parts of micron spherical aluminum nitride, 5 parts of silicon carbide nanowires and 70 parts of bisphenol A epoxy resin, wherein the aspect ratio of the silicon carbide nanowires is about 150, the diameter of the silicon carbide nanowires is 100nm, and the median particle size of the micron spherical aluminum nitride is 1 micron.
(1) Ultrasonically dispersing silicon carbide nanowires and toluene to form a silicon carbide nanowire dispersion liquid, wherein the concentration of the dispersion liquid is 1g/1000 mL;
(2) adding micron spherical aluminum nitride and bisphenol A epoxy resin into the silicon carbide nanowire dispersion liquid, performing ultrasonic dispersion to form a uniform dispersion system, and then performing reduced pressure distillation at 60 ℃ to remove toluene to obtain a solvent-free dispersion system;
(3) adding methyl tetrahydrophthalic anhydride and 2-ethylimidazole (the mass ratio of the methyl tetrahydrophthalic anhydride to the bisphenol A epoxy resin is 40: 100, and the mass ratio of the 2-ethylimidazole to the bisphenol A epoxy resin is 1: 100) into the solvent-free dispersion system, uniformly mixing by using a planetary centrifugal stirrer, carrying out vacuum de-bubbling treatment (15 minutes and 3 times of repetition) at 60 ℃, pre-curing for 0.5 hour at 80 ℃, and post-curing for 8 hours at 170 ℃ to obtain the micro-nano epoxy resin electronic packaging material.
Example 4
Preparing materials according to parts by volume: 60 parts of micron spherical boron nitride, 1 part of silicon carbide nanowires and 39 parts of bisphenol A epoxy resin, wherein the aspect ratio of the silicon carbide nanowires is about 80, the diameter of the silicon carbide nanowires is 70nm, and the median particle size of the micron spherical alumina is 120 microns.
(1) Ultrasonically dispersing silicon carbide nanowires and N, N' -dimethylformamide to form a silicon carbide nanowire dispersion liquid, wherein the concentration of the dispersion liquid is 1g/500 mL;
(2) adding micron spherical boron nitride and bisphenol A epoxy resin into the silicon carbide nanowire dispersion liquid, performing ultrasonic dispersion to form a uniform dispersion system, and then performing reduced pressure distillation at 100 ℃ to remove N, N' -dimethylformamide to obtain a solvent-free dispersion system;
(3) adding pyromellitic anhydride (the mass ratio of the pyromellitic anhydride to the bisphenol A epoxy resin is 80: 100) into the solvent-free dispersion system, uniformly mixing by using a planetary centrifugal stirrer, carrying out vacuum defoaming treatment (15 minutes, repeating for 3 times) at 60 ℃, pre-curing for 2 hours at 100 ℃, and post-curing for 8 hours at 180 ℃ to obtain the micro-nano epoxy resin electronic packaging material.
Example 5
Preparing materials according to parts by volume: 30 parts of micron spherical alumina, 3 parts of silver nanowires and 67 parts of novolac epoxy resin, wherein the aspect ratio of the silver nanowires is about 150, the diameter of the silver nanowires is 70nm, and the median particle size of the micron spherical alumina is 50 microns.
(1) Carrying out ultrasonic dispersion on silver nanowires and tetrahydrofuran to form silver nanowire dispersion liquid, wherein the concentration of the dispersion liquid is 1g/100 mL;
(2) adding micron spherical alumina and novolac epoxy resin into the silver nanowire dispersion liquid, performing ultrasonic dispersion to form a uniform dispersion system, and then performing reduced pressure distillation at 40 ℃ to remove tetrahydrofuran to obtain a solvent-free dispersion system;
(3) adding 2-phenylimidazole (the mass ratio of 2-phenylimidazole to novolac epoxy resin is 2: 100) into the solvent-free dispersion system, uniformly mixing by using a planetary centrifugal stirrer, carrying out vacuum de-bubbling treatment (15 minutes, repeating for 3 times) at 40 ℃, pre-curing for 2 hours at 70 ℃, and post-curing for 5 hours at 180 ℃ to obtain the micro-nano epoxy resin electronic packaging material.
Example 6
Preparing materials according to parts by volume: 40 parts of micron spherical alumina, 1 part of silver nanowires and 59 parts of novolac epoxy resin, wherein the aspect ratio of the silver nanowires is about 150, the diameter of the silver nanowires is 70nm, and the median particle size of the micron spherical alumina is 60 microns.
(1) Carrying out ultrasonic dispersion on silver nanowires and acetone to form silver nanowire dispersion liquid, wherein the concentration of the dispersion liquid is 1g/500 mL;
(2) adding micron spherical alumina and novolac epoxy resin into the silver nanowire dispersion liquid, performing ultrasonic dispersion to form a uniform dispersion system, and then performing reduced pressure distillation at 40 ℃ to remove tetrahydrofuran to obtain a solvent-free dispersion system;
(3) adding low-molecular polyamide (the mass ratio of the low-molecular polyamide to the novolac epoxy resin is 60: 100) into the solvent-free dispersion system, uniformly mixing by using a planetary centrifugal stirrer, carrying out vacuum defoaming treatment (15 minutes, repeating for 3 times) at 40 ℃, pre-curing for 5 hours at 25 ℃, and post-curing for 2 hours at 70 ℃ to obtain the micro-nano epoxy resin electronic packaging material.
Example 7
Preparing materials according to parts by volume: 50 parts of micron spherical alumina, 3 parts of silver nanowires and 47 parts of bisphenol A epoxy resin, wherein the aspect ratio of the silver nanowires is about 100, the diameter of the silver nanowires is 50nm, and the median particle size of the micron spherical alumina is 10 microns.
(1) Carrying out ultrasonic dispersion on silver nanowires and ethanol to form silver nanowire dispersion liquid, wherein the concentration of the dispersion liquid is 1g/100 mL;
(2) adding micron spherical alumina and bisphenol A epoxy resin into the silver nanowire dispersion liquid, performing ultrasonic dispersion to form a uniform dispersion system, and then performing reduced pressure distillation at 40 ℃ to remove ethanol to obtain a solvent-free dispersion system;
(3) adding methyl hexahydrophthalic anhydride and m-xylene diamine (the mass ratio of the methyl hexahydrophthalic anhydride to the bisphenol A epoxy resin is 80: 100, and the mass ratio of the m-xylene diamine to the bisphenol A epoxy resin is 8: 100) into the solvent-free dispersion system, uniformly mixing by using a planetary centrifugal stirrer, performing vacuum de-bubbling treatment (15 minutes and 3 times of repetition) at 60 ℃, pre-curing for 3 hours at 70 ℃, and post-curing for 6 hours at 140 ℃ to obtain the micro-nano epoxy resin electronic packaging material.
Example 8
Preparing materials according to parts by volume: 30 parts of micron spherical alumina, 5 parts of silver nanowires and 65 parts of bisphenol F epoxy resin, wherein the aspect ratio of the silver nanowires is about 200, the diameter of the silver nanowires is 50nm, and the median particle size of the micron spherical alumina is 120 microns.
(1) Carrying out ultrasonic dispersion on silver nanowires and ethanol to form silver nanowire dispersion liquid, wherein the concentration of the dispersion liquid is 1g/500 mL;
(2) adding micron spherical alumina and bisphenol F epoxy resin into the silver nanowire dispersion liquid, performing ultrasonic dispersion to form a uniform dispersion system, and then performing reduced pressure distillation at 40 ℃ to remove ethanol to obtain a solvent-free dispersion system;
(3) and adding triethylene tetramine (the mass ratio of the triethylene tetramine to the bisphenol F type epoxy resin is 60: 100) into the solvent-free dispersion system, uniformly mixing by using a planetary centrifugal stirrer, carrying out vacuum defoaming treatment (15 minutes and 3 times of repetition) at the temperature of 25 ℃, precuring for 3 hours at the temperature of 50 ℃, and post-curing for 2 hours at the temperature of 120 ℃ to obtain the micro-nano epoxy resin electronic packaging material.
Example 9
Preparing materials according to parts by volume: 50 parts of micron spherical aluminum nitride, 5 parts of silicon carbide nanowires and 45 parts of bisphenol A epoxy resin, wherein the aspect ratio of the silicon carbide nanowires is about 80, the diameter of the silicon carbide nanowires is 100nm, and the median particle size of the micron spherical aluminum nitride is 50 microns.
(1) Carrying out ultrasonic dispersion on the silicon carbide nanowires and N, N' -dimethylformamide to form silver nanowire dispersion liquid, wherein the concentration of the dispersion liquid is 1g/500 mL;
(2) adding micron spherical aluminum nitride and bisphenol A epoxy resin into the silver nanowire dispersion liquid, performing ultrasonic dispersion to form a uniform dispersion system, and then performing reduced pressure distillation at 40 ℃ to remove ethanol to obtain a solvent-free dispersion system;
(3) and adding diaminodiphenylmethane (the mass ratio of the diaminodiphenylmethane to the bisphenol A epoxy resin is 25: 100) into the solvent-free dispersion system, uniformly mixing by using a planetary centrifugal stirrer, carrying out vacuum defoaming treatment (15 minutes and 3 times of repetition) at 50 ℃, precuring for 3 hours at 80 ℃, and post-curing for 2 hours at 160 ℃ to obtain the micro-nano epoxy resin electronic packaging material.
Comparative example 1
Adding 2-ethyl-4-methylimidazole into bisphenol F epoxy resin (the mass ratio of 2-ethyl-4-methylimidazole to bisphenol F epoxy resin is 6: 100), uniformly mixing, then carrying out vacuum defoaming treatment, precuring for 2 hours at a low temperature of 60 ℃, and then post-curing for 8 hours at a temperature of 150 ℃ to obtain the pure epoxy resin material.
Comparative example 2
Preparing materials according to parts by volume: 0.5 part of silver nanowires and 99.5 parts of bisphenol F type epoxy resin, wherein the aspect ratio of the silver nanowires is about 125, and the diameter of the silver nanowires is 80 nm;
(1) carrying out ultrasonic dispersion on silver nanowires and ethanol to form silver nanowire dispersion liquid, wherein the concentration of the dispersion liquid is 1g/50 mL;
(2) adding bisphenol F epoxy resin into the silver nanowire dispersion liquid, performing ultrasonic dispersion to form a uniform dispersion system, and then performing reduced pressure distillation at 40 ℃ to remove ethanol to obtain a solvent-free dispersion system;
(3) adding 2-ethyl-4-methylimidazole (the mass ratio of 2-ethyl-4-methylimidazole to bisphenol F type epoxy resin is 6: 100) into the solvent-free dispersion system, uniformly mixing by using a planetary centrifugal stirrer, performing vacuum defoaming treatment (15 minutes and 3 times) at 25 ℃, pre-curing for 2 hours at 60 ℃, and post-curing for 8 hours at 150 ℃ to obtain the silver nanowire/epoxy resin composite material.
Comparative example 3
Preparing materials according to parts by volume: 40 parts of micron spherical alumina and 60 parts of bisphenol F epoxy resin, wherein the median particle size of the micron spherical alumina is 5 mu m.
Adding micron spherical alumina, 2-ethyl-4-methylimidazole and bisphenol F type epoxy resin (the mass ratio of the 2-ethyl-4-methylimidazole to the bisphenol F type epoxy resin is 6: 100) into a planetary centrifugal stirrer to be uniformly mixed, carrying out vacuum de-bubbling treatment (15 minutes and 3 times of repetition) at 25 ℃, then precuring for 2 hours at 60 ℃, and then post-curing for 8 hours at 150 ℃ to obtain the spherical alumina/epoxy resin composite material.
Characterization and results of Performance
Description of the Performance test methods:
(1) heat conductivity: the thermal conductivity of the disc-shaped samples was measured using LFA467 HyperFlash laser flash thermal conductivity apparatus, NETZSCH, Germany, with the test standards ASTM E1461 and ASTM E2585 standards.
(2) Steady state rheological properties: a Brookfield R/S rotational rheometer (Brookfield company in America) is adopted to test the shear viscosity of the epoxy resin and the uncured system of the epoxy resin composite material, a CC-14 coaxial cylindrical rotor is selected, and the shear rate is measured in a range of 0.5-2001/S. The test temperature was controlled to 25 ℃ by a circulating thermostatic water bath system.
(3) Electrical properties: the volume resistivity of the disc-shaped disc was measured using a dielectric resistance tester (TH2684A) from Hokkaido electronics, Inc., test standard GB/T1410-2006.
(4) Coefficient of thermal expansion: TMAQ400EM (American TA instrument) is adopted to test the linear thermal expansion coefficient of the sample, nitrogen atmosphere, the heating rate is 5 ℃/min, 0.1N constant static force is applied to the sample, and the test temperature range is 30-200 ℃.
(5) Mechanical properties: the three point flexural properties of the epoxy resins and composites were tested using an Instron Series 5567 Universal electronic tensile machine (Instron Enstrron Inc., USA) with the test standard GB/T2570-95.
The composite materials obtained in the different examples and comparative examples were subjected to the performance test in the above manner, and the test results are shown in table 1.
TABLE 1 results of performance test of the composite materials obtained in example 1 and comparative examples 1 to 3
As can be seen from table 1, compared with the micron spherical alumina heat-conducting filler/epoxy resin composite material, the micro-nano epoxy resin electronic packaging material of the present invention has the advantages that after a small amount of one-dimensional heat-conducting filler with high length-diameter ratio is introduced, the heat-conducting property of the composite material is significantly improved; although the viscosity is improved, the viscosity of the micro-nano epoxy resin electronic packaging material can still meet the processing requirement, namely the low viscosity of the composite material is maintained. Meanwhile, the micro-nano epoxy resin electronic packaging material has lower thermal expansion coefficient, higher glass transition temperature and better mechanical property on the premise of ensuring good processing flow property and electrical insulating property, is beneficial to improving the thermal management efficiency of electronic devices and improving the working stability and safety of electronic equipment. The material has high application value in the field of high-performance electronic packaging materials.
FIG. 3 is a graph of the shear viscosity versus shear rate at 25 ℃ for composites obtained in example 1 and comparative example 1, and comparative example 2 and comparative example 3. From FIG. 3, it can be seen that the shear rate (10 s) is the same at the same temperature-1) Under the conditions that the viscosity of the neat epoxy resin (comparative example 1) was 2.8Pa · s, the shear viscosity of the epoxy resin/silver nanowire composite (comparative example 2) containing 0.5 vol.% silver nanowires was 3.8Pa · s, 40 vol.% loading of spherical alumina/ringsThe shear viscosity of the oxygen resin composite (comparative example 3) was 35.6Pa · s, while the shear viscosity of the micro-nano epoxy resin composite (example 1) containing both 0.5 vol.% silver nanowires and 40 vol.% spherical alumina was 55.6Pa · s. Although the shear viscosity of example 1 was slightly greater than that of comparative example 3, the difference between the two composites was mainly due to the difference between the pure epoxy and the epoxy/silver nanowire composite. After a small amount of silver nanowires are introduced into the micron epoxy resin composite material, the viscosity of the composite material does not show obvious synergistic increase, low viscosity and good flow property are still maintained, and the processing requirement of an electronic packaging process can be met.
Similarly, the micro-nano epoxy resin electronic packaging materials obtained in the embodiments 2 to 9 can be observed by a section scanning electron microscope, and the nano one-dimensional heat-conducting filler can be dispersed in the micro spherical heat-conducting filler. Meanwhile, the micro-nano epoxy resin electronic packaging materials obtained in the embodiments 2-9 are tested for heat conductivity and viscosity performance, so that the low viscosity of the composite material can be maintained, and the heat conductivity is remarkably improved on the premise of meeting the processing requirement; from the above, the composite material provided by the invention can meet the requirements on the viscosity and the heat conductivity of the packaging material, and is suitable for electronic packaging.
Although the above embodiments have been described in detail, they are only a part of the embodiments of the present invention, not all of the embodiments, and other embodiments can be obtained without inventive step according to the embodiments, and all of the embodiments belong to the protection scope of the present invention.
Claims (10)
1. A micro-nano epoxy resin electronic packaging material is prepared from the following raw materials in parts by volume: 25-60 parts of micron spherical heat-conducting filler, 0.5-5 parts of nano one-dimensional heat-conducting filler and 30-75 parts of epoxy resin.
2. The micro-nano epoxy resin electronic packaging material of claim 1, wherein the micro-nano spherical heat conductive filler is one or more of spherical aluminum oxide, spherical aluminum nitride and spherical boron nitride; the nano one-dimensional heat-conducting filler is a silver nanowire and/or a silicon carbide nanowire.
3. The micro-nano epoxy resin electronic packaging material of claim 1 or 2, wherein the aspect ratio of the nano one-dimensional heat conductive filler is greater than or equal to 80.
4. The micro-nano epoxy resin electronic packaging material of claim 1 or 2, wherein the micron spherical heat conductive filler has a median particle size of 1-120 μm.
5. The micro-nano epoxy resin electronic packaging material of claim 1, wherein the epoxy resin comprises one or a mixture of any of bisphenol A epoxy resin, bisphenol F epoxy resin and novolac epoxy resin.
6. The preparation method of the micro-nano epoxy resin electronic packaging material of any one of claims 1 to 5, comprising the following steps:
(1) dispersing the nanometer one-dimensional heat-conducting filler in an organic solvent to obtain nanometer one-dimensional heat-conducting filler dispersion liquid;
(2) dispersing the micron spherical heat-conducting filler and the epoxy resin in the nano one-dimensional heat-conducting filler dispersion liquid, and then removing the organic solvent through reduced pressure distillation to obtain a solvent-free dispersion system;
(3) and curing and molding the solvent-free dispersion system to obtain the micro-nano epoxy resin electronic packaging material.
7. The method according to claim 6, wherein the organic solvent in step (1) comprises one or more of methanol, ethanol, acetone, tetrahydrofuran, toluene, and N, N' -dimethylformamide.
8. The method according to claim 6, wherein the curing agent for curing molding comprises one or more of 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, methylhexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, pyromellitic anhydride, triethylenetetramine, m-xylylenediamine, diaminodiphenylmethane, and polyamide curing agent.
9. The preparation method according to claim 6 or 8, wherein the curing and forming in step (3) comprises pre-curing and post-curing in sequence, wherein the pre-curing temperature is 25-120 ℃ and the time is 0.5-5 hours; the post-curing temperature is 70-180 ℃, and the time is 2-8 hours.
10. The micro-nano epoxy resin electronic packaging material of any one of claims 1 to 5 or the micro-nano epoxy resin electronic packaging material obtained by the preparation method of any one of claims 6 to 9 is applied to electronic packaging.
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Application publication date: 20210122 |