CN115595102A - Epoxy resin composition glue solution, preparation method thereof, adhesive film and application - Google Patents
Epoxy resin composition glue solution, preparation method thereof, adhesive film and application Download PDFInfo
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- CN115595102A CN115595102A CN202211215244.2A CN202211215244A CN115595102A CN 115595102 A CN115595102 A CN 115595102A CN 202211215244 A CN202211215244 A CN 202211215244A CN 115595102 A CN115595102 A CN 115595102A
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- epoxy resin
- resin composition
- heat
- glue solution
- mass
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 200
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 200
- 239000000203 mixture Substances 0.000 title claims abstract description 75
- 239000003292 glue Substances 0.000 title claims abstract description 53
- 239000002313 adhesive film Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000000843 powder Substances 0.000 claims abstract description 103
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims abstract description 40
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 claims abstract description 39
- 239000002904 solvent Substances 0.000 claims abstract description 35
- 229910052582 BN Inorganic materials 0.000 claims abstract description 33
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000004305 biphenyl Substances 0.000 claims abstract description 20
- 235000010290 biphenyl Nutrition 0.000 claims abstract description 20
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 19
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 44
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 29
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 claims description 24
- 239000000463 material Substances 0.000 claims description 24
- 239000002245 particle Substances 0.000 claims description 24
- 239000013078 crystal Substances 0.000 claims description 21
- 239000012452 mother liquor Substances 0.000 claims description 20
- 238000002156 mixing Methods 0.000 claims description 17
- 229910052751 metal Inorganic materials 0.000 claims description 16
- 239000002184 metal Substances 0.000 claims description 16
- 238000004513 sizing Methods 0.000 claims description 14
- 239000000758 substrate Substances 0.000 claims description 14
- 239000002113 nanodiamond Substances 0.000 claims description 13
- 239000005011 phenolic resin Substances 0.000 claims description 12
- 238000000498 ball milling Methods 0.000 claims description 11
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 10
- 125000003700 epoxy group Chemical group 0.000 claims description 10
- 229920001568 phenolic resin Polymers 0.000 claims description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 239000004850 liquid epoxy resins (LERs) Substances 0.000 claims 1
- 238000010292 electrical insulation Methods 0.000 abstract description 11
- 230000000052 comparative effect Effects 0.000 description 21
- 230000000694 effects Effects 0.000 description 15
- 230000017525 heat dissipation Effects 0.000 description 11
- 239000006185 dispersion Substances 0.000 description 9
- 230000015556 catabolic process Effects 0.000 description 8
- 239000000539 dimer Substances 0.000 description 8
- 239000010410 layer Substances 0.000 description 8
- 230000008569 process Effects 0.000 description 7
- JRQJLSWAMYZFGP-UHFFFAOYSA-N 1,1'-biphenyl;phenol Chemical compound OC1=CC=CC=C1.C1=CC=CC=C1C1=CC=CC=C1 JRQJLSWAMYZFGP-UHFFFAOYSA-N 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000005054 agglomeration Methods 0.000 description 5
- 230000002776 aggregation Effects 0.000 description 5
- 229920001971 elastomer Polymers 0.000 description 5
- 239000011342 resin composition Substances 0.000 description 5
- 230000002195 synergetic effect Effects 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 239000000919 ceramic Substances 0.000 description 4
- 239000000945 filler Substances 0.000 description 4
- 238000009775 high-speed stirring Methods 0.000 description 4
- 239000005416 organic matter Substances 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 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 3
- 238000007731 hot pressing Methods 0.000 description 3
- 238000010561 standard procedure Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- 229930185605 Bisphenol Natural products 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 2
- 239000004842 bisphenol F epoxy resin Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 229910000679 solder Inorganic materials 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 238000003466 welding Methods 0.000 description 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 239000004844 aliphatic epoxy resin Substances 0.000 description 1
- 150000001343 alkyl silanes Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000002619 bicyclic group Chemical group 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000005219 brazing Methods 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000011231 conductive filler Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 229920006038 crystalline resin Polymers 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000004845 glycidylamine epoxy resin Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000004843 novolac epoxy resin Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 230000009044 synergistic interaction Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- AAAQKTZKLRYKHR-UHFFFAOYSA-N triphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/205—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase
- C08J3/21—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase the polymer being premixed with a liquid phase
- C08J3/215—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase the polymer being premixed with a liquid phase at least one additive being also premixed with a liquid phase
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K7/00—Constructional details common to different types of electric apparatus
- H05K7/20—Modifications to facilitate cooling, ventilating, or heating
- H05K7/2039—Modifications to facilitate cooling, ventilating, or heating characterised by the heat transfer by conduction from the heat generating element to a dissipating body
- H05K7/20509—Multiple-component heat spreaders; Multi-component heat-conducting support plates; Multi-component non-closed heat-conducting structures
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
- C08J2363/02—Polyglycidyl ethers of bis-phenols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2463/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2463/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
- C08J2463/02—Polyglycidyl ethers of bis-phenols
-
- 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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/28—Nitrogen-containing compounds
- C08K2003/282—Binary compounds of nitrogen with aluminium
-
- 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
- C08K2003/385—Binary compounds of nitrogen with boron
-
- 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
- C08K2201/005—Additives being defined by their particle size in general
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
Abstract
The invention relates to an epoxy resin composition glue solution, a preparation method thereof, a bonding film and application. The epoxy resin composition glue solution comprises an epoxy resin composition and a solvent, wherein the epoxy resin composition comprises heat-conducting powder, epoxy resin and a curing agent, and the mass fraction of the heat-conducting powder in the epoxy resin composition is more than or equal to 90%; the heat conducting powder comprises aluminum oxide, boron nitride, aluminum nitride and nano heat conducting powder with the heat conductivity coefficient more than or equal to 500W/m.K; the epoxy resin comprises 40-65 wt% of first epoxy resin and 35-60 wt% of second epoxy resin, the first epoxy resin is epoxy resin with viscosity less than or equal to 5000cps at 25 ℃ in a non-solvent type state, and the second epoxy resin comprises crystalline epoxy resin and biphenyl type epoxy resin. The adhesive film prepared from the epoxy resin composition is high in heat conductivity coefficient, and excellent in fluidity, peeling strength and electrical insulation.
Description
Technical Field
The invention relates to the technical field of polymer composite materials, in particular to an epoxy resin composition glue solution, a preparation method thereof, a bonding film and application thereof.
Background
In recent years, with the higher automation degree of new energy automobiles, the higher integration effect and the higher power requirement on electronic devices are. Especially, for a packaged chip on a power module in an automobile controller, the stability and reliability of the packaged chip are very important. When the heat generated by the chip is not conducted out in time, the component will fail due to long-term heat accumulation.
In the traditional technology, a direct copper clad ceramic substrate (DBC) material or an active metal brazing copper clad ceramic substrate (AMB) material is usually combined with a heat sink for heat dissipation of a chip, but in the DBC material and the AMB material, because the ceramic substrate and a metal plate are packaged by a tin paste layer with a certain thickness, welding gaps and multilayer interface conditions exist, and interface thermal resistance is increased; the long-term use of the solder paste can cause the cracking risk of the solder paste, so that the thermal resistance is gradually improved. In order to optimize the scheme, the traditional technology is improved, the adhesive film with good fluidity is prepared by using the glue solution prepared from the resin composition containing the heat-conducting powder, the corresponding high-heat-conducting metal substrate is directly used or prepared under the specific power condition to replace a ceramic substrate, and the self-packaging can be realized with the metal plate, so that the welding layer is reduced, the packaging thickness is reduced, the heat dissipation path is shortened, and the heat dissipation effect is favorably improved.
The method for improving the heat conductivity of the adhesive film is often realized by increasing the content of the heat conductive powder in the resin composition. However, as the mass fraction of the heat-conducting powder in the resin composition increases, the viscosity of the heat-conducting powder in the resin composition adhesive solution increases sharply, the dispersion effect is poor, and the fluidity of the adhesive film made of the resin composition adhesive solution is poor, so that the adhesive film has a stitching cavity, and the problems of low peeling strength, poor electrical insulation performance and the like are caused.
Disclosure of Invention
In view of the above, there is a need to provide an epoxy resin composition adhesive solution, a preparation method thereof, an adhesive film and applications thereof; the dispersion of the heat-conducting powder in the epoxy resin composition glue solution is improved while the high mass fraction of the heat-conducting powder in the epoxy resin composition is ensured, so that the prepared adhesive film has high heat conductivity coefficient, and excellent fluidity, peel strength and electrical insulation property.
An epoxy resin composition glue solution comprises an epoxy resin composition and a solvent, wherein the epoxy resin composition comprises heat-conducting powder, epoxy resin and a curing agent, and the mass fraction of the heat-conducting powder in the epoxy resin composition is more than or equal to 90%;
the heat conducting powder comprises aluminum oxide, boron nitride, aluminum nitride and nano heat conducting powder with the heat conducting coefficient larger than or equal to 500W/m.K, and the mass ratio of the nano heat conducting powder, the boron nitride, the aluminum nitride and the aluminum oxide is (0.5-2): 5-20): 550-750): 400-600;
the epoxy resin comprises 40-65 wt% of first epoxy resin and 35-60 wt% of second epoxy resin, wherein the first epoxy resin is selected from epoxy resin with viscosity less than or equal to 5000cps in a non-solvent type state at 25 ℃, the second epoxy resin comprises crystalline epoxy resin and biphenyl epoxy resin, and the structural formula of the crystalline epoxy resin is shown in the specification
In one embodiment, D of the nano heat-conducting powder 50 8nm-200nm;
and/or D of said alumina 50 Is 0.1 μm to 40 μm;
and/or D of said boron nitride 50 20-65 μm;
and/or D of said aluminum nitride 50 Is 30-80 μm.
In one embodiment, the nano heat conductive powder is selected from nano diamond;
and/or the alumina is selected from single crystal alumina, and alpha phase of the single crystal alumina is greater than or equal to 98%;
and/or the boron nitride is selected from spherical boron nitride;
and/or the aluminum nitride is selected from spherical aluminum nitride, and the spherical aluminum nitride is treated by a silane coupling agent, wherein the silane coupling agent at least comprises a nonpolar silane coupling agent and a silane coupling agent containing an epoxy group, and the carbon atom number of alkyl in the nonpolar silane coupling agent is selected from 1 to 12.
In one embodiment, the spherical aluminum nitride has a breakage rate of less than 1%.
In one embodiment, the epoxy resin with the viscosity of less than or equal to 5000cps in a non-solvent state at 25 ℃ is selected from at least one of bisphenol A epoxy resin, bisphenol F epoxy resin and acrylic modified epoxy resin.
In one embodiment, the mass ratio of the crystalline epoxy resin to the biphenyl epoxy resin is 0.25.
In one embodiment, the curing agent at least comprises biphenyl type phenolic resin, and the mass fraction of the biphenyl type phenolic resin in the curing agent is more than 50%.
The preparation method of the epoxy resin composition glue solution comprises the following steps:
mixing heat-conducting powder with the particle size of less than or equal to 1 mu m, part of first epoxy resin and part of solvent for primary ball milling to obtain fine powder mother liquor;
mixing the rest of the first epoxy resin, the rest of the second epoxy resin, the curing agent and the rest of the solvent to obtain a mixed rubber material; and
mixing the heat-conducting powder with the grain diameter of more than 1 mu m and less than 20 mu m, the fine powder mother liquor and the mixed glue stock, performing secondary ball milling, and mixing with the heat-conducting powder with the grain diameter of more than or equal to 20 mu m to obtain the epoxy resin composition glue solution.
In one embodiment, in the epoxy resin composition glue solution, the amount of the part of the first epoxy resin accounts for 10% -20% of the total mass of the first epoxy resin in the epoxy resin composition glue solution.
An adhesive film was prepared from the epoxy resin composition glue solution as described above.
An adhesive film as described above is used for preparing a heat-dissipating metal substrate.
In the epoxy resin composition, boron nitride, aluminum oxide and nano heat-conducting powder with the heat conductivity coefficient of more than or equal to 500W/mK are quantitatively combined, and are compounded with the first epoxy resin and the second epoxy resin with specific viscosity and structure types to generate a synergistic effect of a specific composition mixing mode, so that the epoxy resin composition has a good dispersion effect while containing more than 90% of heat-conducting powder, and has excellent heat-conducting effect, peeling strength and electric insulation property.
Furthermore, in the bonding film prepared by adopting the epoxy resin composition glue solution, through the collocation of organic structures, the cured organic matters have good structural regularity, so that a good heat conduction organic channel is established, the organic channel is synergistic with high heat conduction powder of a specific type and a specific particle size, the heat conduction coefficient of the bonding film is more than or equal to 8.0W/m.K, the fluidity is more than or equal to 15%, the peel strength under the standard thickness of 1oz is more than 10.5N/cm, and the bonding film has good electrical insulation property. Therefore, when the bonding film is used for preparing a heat dissipation metal substrate, the heat dissipation metal substrate has good heat dissipation effect, peeling strength and electrical insulation, and further can meet higher practical application requirements.
Detailed Description
In order to facilitate an understanding of the invention, the invention will now be described in more detail. It should be understood, however, that the present invention may be embodied in many different forms and should not be construed as being limited to the embodiments or examples set forth herein. Rather, these embodiments or examples are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments or examples only and is not intended to be limiting of the invention.
The epoxy resin composition glue solution provided by the invention comprises an epoxy resin composition and a solvent, wherein the epoxy resin composition comprises heat-conducting powder, epoxy resin and a curing agent, and the mass fraction of the heat-conducting powder in the epoxy resin composition is greater than or equal to 90%.
Specifically, the heat conducting powder comprises aluminum oxide, boron nitride, aluminum nitride and nano heat conducting powder with the heat conductivity coefficient larger than or equal to 500W/m.K, and the mass ratio of the nano heat conducting powder, the boron nitride, the aluminum nitride and the aluminum oxide is (0.5-2): 5-20): 550-750): 400-600.
Therefore, the invention quantitatively combines boron nitride, aluminum oxide and nano heat-conducting powder with the heat conductivity coefficient of more than or equal to 500W/mK, and improves the heat conductivity coefficient of the heat-conducting powder through synergistic interaction, thereby improving the heat conductivity coefficient of the bonding film.
On one hand, in order to fully fill gaps among large particles with small particles to improve the dispersion effect, the built heat-conducting powder has excellent stacking compactness, so that the filling effect of the heat-conducting powder in the adhesive film is improved, and the heat conductivity coefficient of the adhesive film is further improved; on the other hand, the nanometer heat-conducting powder with specific shape, particle size and specific proportion is beneficial to the lubricating flow of the heat-conducting powder in the composition in the hot pressing process, can reduce the viscosity of the glue solution of the epoxy resin composition, thereby improving the fluidity, the peeling strength and the insulating property of the bonding film, and preferably, the D of the nanometer heat-conducting powder 50 Is 8nm to 200nm, D of the alumina 50 0.1 μm to 40 μm, D of said boron nitride 50 20 μm to 65 μm, D of the aluminum nitride 50 Is 30-80 μm.
In order to improve the agglomeration problem of the nanometer heat conducting powder and enable the nanometer heat conducting powder to be dispersed more uniformly, the nanometer heat conducting powder with positive charges on the surface is more preferable.
Specifically, the processing mode for making the surface of the nano heat conducting powder positively charged is selected from R-H or R-NH 2 Positive charge treatment.
Preferably, the nano heat conducting powder is selected from nano diamond.
In particular, the alumina is selected from single crystal aluminas. To further improve the heat transfer capability, the alpha phase of the single crystal alumina is greater than or equal to 98%.
In order to realize the effect of accurate filling under the condition of high proportion of the single crystal alumina, the built heat-conducting powder has more excellent stacking compactness, and the D of the single crystal alumina is optimized 50 Is 0.1 μm to 20 μm, more preferably 0.5 μm to 10 μm.
Compared with scale-shaped boron nitride, the spherical boron nitride has more uniform heat transfer capacities and lower oil absorption rate, and can relieve the viscosity increase of the epoxy resin composition caused by the filling proportion of the high-heat-conduction powder, so that the peel strength of the bonding film prepared from the epoxy resin composition glue solution is improved, and therefore, the boron nitride is preferably the spherical boron nitride.
Because of its active nature, aluminum nitride reacts easily with water vapor in air and is transformed into Al (OH) 3 Resulting in performance changes and a substantial decrease in the thermal conductivity of the aluminum nitride. Therefore, spherical aluminum nitride surface-treated with a silane coupling agent is preferable.
In order to improve the compatibility with the epoxy resin and the peeling strength and the fluidity of the adhesive film while making the aluminum nitride water-proof, the silane coupling agent at least comprises a non-polar silane coupling agent and a silane coupling agent containing an epoxy group, wherein the carbon atom number of the alkyl in the non-polar silane coupling agent is 1-12.
Specifically, the surface of the aluminum nitride is coated with a nonpolar silane coupling agent, and then the silane coupling agent containing epoxy groups is further modified.
Preferably, the spherical aluminum nitride surface-treated with the silane coupling agent has a surface activation index R =0.98 to 1, more preferably R =1.
In order to provide aluminum nitride with a more suitable specific surface area, spherical aluminum nitride having a breakage rate of less than 1% is preferred.
Specifically, the epoxy resin comprises 40-65 wt% of first epoxy resin and 35-60 wt% of second epoxy resin, wherein the first epoxy resin is selected from epoxy resins with viscosity of less than or equal to 5000cps in a 25 ℃ non-solvent type state, the second epoxy resin comprises crystalline epoxy resin and biphenyl epoxy resin, and the structural formula of the crystalline epoxy resin is shown in the specification
Therefore, the first epoxy resin and the second epoxy resin which have specific viscosity and structure type selection are compounded to generate a synergistic effect, so that on one hand, organic heat conduction channels of the epoxy resins can be more ordered, the transmission speed of heat in the epoxy resins is increased, and the heat conduction effect of the bonding film is better; on the other hand, the flow wettability of the epoxy resin and the heat-conducting filler can be improved, so that the adhesive film has higher fluidity, the epoxy resin composition can effectively flow in the hot-pressing using process, the defects such as fine cracks, cavities and the like in the adhesive film can be fully filled and leveled in the process, the adhesive film can be ensured to have good electrical insulation property, and the peeling strength can be favorably improved.
Preferably, the mass ratio of the crystalline epoxy resin to the biphenyl epoxy resin is 0.25.
Specifically, the first epoxy resin is selected from at least one of bisphenol A epoxy resin, bisphenol F epoxy resin and acrylic modified epoxy resin.
Therefore, in the epoxy resin composition, boron nitride, aluminum oxide and nano heat conduction powder with the heat conduction coefficient of more than or equal to 500W/m.K are quantitatively combined, and are compounded with the first epoxy resin and the second epoxy resin with specific viscosity and selected structure types to generate a synergistic effect, so that the epoxy resin composition has a good dispersion effect while containing more than 90% of heat conduction powder, and has excellent heat conduction effect, peeling strength and electrical insulation property.
Furthermore, in the adhesive film prepared from the epoxy resin composition glue solution, the cured organic matter has good structural regularity through the collocation of organic matter structures, so that a good heat conduction organic channel is established, and the organic matter and the high heat conduction powder with specific types and particle sizes are synergistic, so that the adhesive film has a high heat conduction coefficient, and is excellent in glue flowing capacity, peeling strength and electrical insulation.
In some embodiments, the epoxy resin further includes a third epoxy resin, and the third epoxy resin is at least one selected from aromatic epoxy resin, aliphatic epoxy resin, alicyclic epoxy resin, and glycidyl ether epoxy resin, and specifically includes at least one selected from bisphenol epoxy resin, novolac epoxy resin, naphthalene epoxy resin, fluorene epoxy resin, triphenylmethane epoxy resin, dimer acid-modified bisphenol epoxy resin, bicyclic epoxy resin, and glycidylamine epoxy resin.
In order to further improve the regularity of the cured organic matter, the curing agent at least comprises biphenyl type phenolic resin, specifically, the ratio of the equivalent of the group capable of reacting with the epoxy group in the curing agent to the equivalent of the epoxy in the epoxy resin is 0.8-1.2, and the mass fraction of the biphenyl type phenolic resin in the curing agent is more than 50%.
Furthermore, the curing agent also comprises at least one of an amine curing agent and an anhydride curing agent.
In order to disperse the heat-conducting powder and adjust the viscosity of the epoxy resin composition, the solvent is at least one selected from butanone, xylene, N-dimethylformamide and ethylene glycol monomethyl ether.
In some embodiments, the epoxy resin composition further comprises an auxiliary agent, which may be selected according to the properties of the epoxy resin composition to be improved, and specifically comprises a dispersant, a leveling agent, a coupling agent, and the like.
The invention provides a preparation method of the epoxy resin composition glue solution, which comprises the following steps:
s1, mixing heat-conducting powder with the particle size of less than or equal to 1 mu m, part of first epoxy resin and part of solvent for primary ball milling to obtain fine powder mother liquor;
s2, mixing the residual first epoxy resin, the residual second epoxy resin, the curing agent and the residual solvent to obtain a mixed rubber material; and
and S3, mixing the heat-conducting powder with the particle size of more than 1 mu m and less than 20 mu m, the fine powder mother liquor and the mixed sizing material, performing secondary ball milling, and mixing with the heat-conducting powder with the particle size of more than or equal to 20 mu m to obtain the epoxy resin composition glue solution.
In the step S1, through a grading dispersion process, firstly, mixing and ball-milling the heat-conducting powder with the particle size of less than or equal to 1 mu m, part of the first epoxy resin and part of the solvent, on one hand, the nano-scale and submicron-scale heat-conducting powder can be uniformly dispersed, and then, when the nano-scale and submicron-scale heat-conducting powder is subjected to high-speed shearing and ball-milling together with other heat-conducting powder with larger particle size, large-particle and undispersed powder packets are not easily formed, the complete uniform dispersion of the heat-conducting powder is ensured, and the application performance of subsequent products is improved; on the other hand, the viscosity of the first epoxy resin is low, and the heat-conducting powder with the grain diameter less than or equal to 1 mu m can realize a better dispersion effect by adopting part of the first epoxy resin.
Preferably, the amount of the part of the first epoxy resin accounts for 10-20% of the total mass of the first epoxy resin in the glue solution of the epoxy resin composition.
Specifically, the rotation speed of the primary ball milling is 600-800 r/min, and the time is 30-45 minutes.
In step S2, in order to make the mixed rubber material have a suitable viscosity, the remaining first epoxy resin, the second epoxy resin, the curing agent and the remaining solvent are mixed to obtain the mixed rubber material.
In step S1 and step S2, the amount of the solvent used in the two steps is not limited, and the dispersing effect may be achieved.
In the step S3, a grading dispersion process is further adopted, so that the problems of large particle powder crushing and the like caused in the process of ball milling of large particle powder and small particle powder together can be effectively avoided, and D is ensured 50 The breaking rate of the heat-conducting powder of more than or equal to 30 is less than or equal to 5 percent, thereby ensuring that the epoxy resin composition filled with the high heat-conducting powder keeps good performance.
In some embodiments, the secondary ball milling is performed at a speed of 400 rpm to 600 rpm for a period of 20 minutes to 30 minutes.
The invention also provides an adhesive film prepared from the epoxy resin composition glue solution.
The adhesive film prepared by the epoxy resin composition glue solution has the heat conductivity coefficient of more than or equal to 8.0W/m.K, the fluidity of more than or equal to 15 percent, the peel strength under the standard thickness of 1oz of more than 10.5N/cm, and good electrical insulation.
In some embodiments, the adhesive film can be coated on a carrier by a conventional coating method, and dried to remove the solvent, thereby obtaining the adhesive film.
Specifically, a comma scraper with a specific thickness is adopted to coat a heat-conducting adhesive layer on a release film, and the release film is kept still and baked to remove the solvent, so that the adhesive film with the thickness of 80-200 μm is obtained.
In the present invention, the method of coating and the carrier to be coated are not specifically limited, and may be any method that satisfies the requirement of producing an adhesive film.
The invention also provides the adhesive film for preparing the heat dissipation metal substrate.
The adhesive film is used for preparing a heat dissipation metal substrate, so that the heat dissipation metal substrate can achieve good heat dissipation effect and electrical insulation, and the high practical application requirement is met.
In some embodiments, a heat dissipating metal substrate includes an adhesive film and a metal layer disposed on at least one surface of the adhesive film.
Specifically, the metal layer is selected from at least one of copper foil, copper plate, and aluminum plate.
In some embodiments, the adhesive film and the metal layer form a layer structure, and the layer structure is hot-pressed at 180-220 ℃ and 40kg/cm by a vacuum press 2 -80kg/cm 2 And carrying out hot-pressing curing for 180-220 min to obtain the heat-dissipation metal substrate.
Hereinafter, the epoxy resin composition glue solution, the preparation method thereof, the adhesive film and the application will be further described by the following specific examples.
Example 1
0.825 parts by mass of nanodiamond (D) 50 =8 nm), 82.5 parts by mass of monocrystalline aluminium oxide (D) 50 =0.8 μm, alpha phase = 98.5%), 10 parts by mass of bisphenol F type epoxy resin (4500cps @25 ℃) and a part of solvent were mixed, and ball-milled at 800 rpm for 45 minutes to obtain a fine powder mother liquor.
50 parts by mass of bisphenol F type epoxy resin (4500 cps @25 ℃), 20 parts by mass of biphenyl type epoxy resin, 20 parts by mass of crystalline type epoxy resin, 65 parts by mass of biphenyl phenol type phenolic resin, and the remaining solvent were mixed to obtain a mixed rubber material.
Firstly, the fine powder mother liquor and the mixed sizing material are mixed and dispersed at high speed, and then 577.5 parts by mass of single crystal alumina (D) is added 50 =10 μm, alpha phase = 98%) was ball-milled at 600 rpm for 30 minutes, and 33 parts by mass of spherical boron nitride (D) was added 50 =25 μm) and 907.5 parts by mass of spherical aluminum nitride (D) surface-treated with a nonpolar silane coupling agent and an epoxy group-containing silane coupling agent in this order 50 =30 μm, breakage = 0.8%), followed by high-speed stirring, low-speed stirring, defoaming, and filtering to obtain an epoxy resin composition glue solution.
Example 2
1.49 parts by mass of nanodiamond (D) 50 =200 nm), 74.5 parts by mass of monocrystalline aluminium oxide (D) 50 =0.5 μm, alpha phase = 98.5%), 10 parts by mass of bisphenol F type epoxy resin (4500cps @25 ℃) and a part of solvent were mixed, and ball-milled at 800 rpm for 45 minutes to obtain a fine powder mother liquor.
40 parts by mass of bisphenol F type epoxy resin (4500cps @25 ℃), 32 parts by mass of biphenyl type epoxy resin, 8 parts by mass of crystalline type epoxy resin, 10 parts by mass of dimer acid-modified bisphenol type epoxy resin, 49 parts by mass of biphenyl phenol type phenolic resin, and the rest of the solvent were mixed to obtain a mixed sizing material.
Firstly, the fine powder mother liquor and the mixed sizing material are mixed and dispersed at high speed, and then 223.5 parts by mass of single crystal alumina (D) is added 50 =3 μm, alpha phase = 98%), 447 parts by mass of single crystal alumina (D) 50 =10 μm, alpha phase = 98%) was ball-milled at 600 rpm for 30 minutes, and 14.9 parts by mass of spherical boron nitride (D) was added 50 =50 μm) and 819.5 parts by mass of spherical aluminum nitride (D) surface-treated with a nonpolar silane coupling agent and an epoxy group-containing silane coupling agent in this order 50 =30 μm, and the breakage = 0.8%), and finally, defoaming and filtering the mixture by low-speed stirring to obtain an epoxy resin composition glue solution.
Example 3
2.28 parts by mass of nanodiamond (D) 50 =200 nm), 152 parts by mass of a single crystal alumina (D) 50 =0.5 μm, alpha phase = 98.5%), 10 parts by massBisphenol F type epoxy resin (4500cps @25 deg.C) and partial solvent are mixed, and ball-milled for 45 min at 800 rpm to obtain fine powder mother liquor.
40 parts by mass of bisphenol F type epoxy resin (4500cps @25 ℃ C.), 33.75 parts by mass of biphenyl type epoxy resin, 11.25 parts by mass of crystalline type epoxy resin, 5 parts by mass of dimer acid-modified bisphenol type epoxy resin, 52 parts by mass of biphenyl phenol type phenol resin, and the rest of the solvent were mixed to obtain a mixed sizing material.
Firstly, mixing the fine powder mother liquor with the mixed sizing material, dispersing at a high speed, and then adding 608 parts by mass of single crystal alumina (D) 50 =10 μm, alpha phase = 98%) was ball-milled at 600 rpm for 30 minutes, and 22.8 parts by mass of spherical boron nitride (D) was added 50 =25 μm) and 912 parts by mass of spherical aluminum nitride (D) surface-treated with a nonpolar silane coupling agent and an epoxy group-containing silane coupling agent in this order 50 =30 μm, and the breakage = 0.8%), and finally, defoaming and filtering the mixture by low-speed stirring to obtain an epoxy resin composition glue solution.
Example 4
1.49 parts by mass of nanodiamond (D) 50 =200 nm), 74.5 parts by mass of monocrystalline aluminium oxide (D) 50 =0.5 μm, alpha phase = 98.5%), 10 parts by mass of bisphenol F type epoxy resin (4500cps @25 ℃) and a part of solvent were mixed, and ball-milled at 800 rpm for 45 minutes to obtain a fine powder mother liquor.
40 parts by mass of bisphenol F type epoxy resin (4500cps @25 ℃), 20 parts by mass of biphenyl type epoxy resin, 15 parts by mass of crystalline type epoxy resin, 15 parts by mass of dimer acid-modified bisphenol type epoxy resin, 49 parts by mass of biphenyl phenol type phenolic resin, and the rest of the solvent were mixed to obtain a mixed sizing material.
Firstly, mixing the fine powder mother liquor with the mixed sizing material, dispersing at a high speed, and then adding 74.5 parts by mass of single crystal alumina (D) 50 =3 μm, alpha phase = 98%), 596 parts by mass of single crystal alumina (D) 50 =10 μm, alpha phase = 98%) was ball-milled at 600 rpm for 30 minutes, and 14.9 parts by mass of spherical boron nitride (D) was added 50 =65 mu m) and 1043 parts by mass of the components sequentially pass through a nonpolar silane coupling agent and silane containing an epoxy groupSpherical aluminum nitride (D) surface-treated with coupling agent 50 =30 μm, breakage = 0.8%), followed by high-speed stirring, low-speed stirring, defoaming, and filtering to obtain an epoxy resin composition glue solution.
Example 5
2.9 parts by mass of nanodiamond (D) 50 =200 nm), 72.5 parts by mass of monocrystalline aluminium oxide (D) 50 =0.8 μm, alpha phase = 98.5%), 10 parts by mass of bisphenol F type epoxy resin (4500cps @25 ℃) and a part of solvent were mixed, and ball-milled at 800 rpm for 45 minutes to obtain a fine powder mother liquor.
30 parts by mass of bisphenol F type epoxy resin (4500cps @25 ℃), 30 parts by mass of biphenyl type epoxy resin, 20 parts by mass of crystalline type epoxy resin, 10 parts by mass of dimer acid-modified bisphenol type epoxy resin, 45 parts by mass of biphenyl phenol type phenolic resin, and the rest of the solvent were mixed to obtain a mixed sizing material.
Firstly, mixing the fine powder mother liquor with the mixed sizing material, dispersing at a high speed, and then adding 217.5 parts by mass of single crystal alumina (D) 50 =3 μm, alpha phase = 98%), 580 parts by mass of monocrystalline alumina (D) 50 =10 μm, alpha phase = 98%) was ball-milled at 600 rpm for 30 minutes, and 7.25 parts by mass of spherical boron nitride (D) was added 50 =50 μm) and 1087.5 parts by mass of spherical aluminum nitride (D) surface-treated with a nonpolar silane coupling agent and an epoxy group-containing silane coupling agent in this order 50 =30 μm, breakage = 0.8%), followed by high-speed stirring, low-speed stirring, defoaming, and filtering to obtain an epoxy resin composition glue solution.
Example 6
1.49 parts by mass of nanodiamond (D) 50 =200 nm), 74.5 parts by mass of monocrystalline aluminium oxide (D) 50 =0.5 μm, alpha phase = 98.5%), 10 parts by mass of bisphenol F type epoxy resin (4500cps @25 ℃) and a part of solvent were mixed, and ball-milled at 800 rpm for 45 minutes to obtain a fine powder mother liquor.
40 parts by mass of bisphenol F type epoxy resin (4500cps @25 ℃), 17.5 parts by mass of biphenyl type epoxy resin, 17.5 parts by mass of crystalline type epoxy resin, 15 parts by mass of dimer acid-modified bisphenol type epoxy resin, 49 parts by mass of biphenyl phenol type phenol resin, and the rest of the solvent were mixed to obtain a mixed sizing material.
Firstly, the fine powder mother liquor and the mixed sizing material are mixed and dispersed at high speed, and then 223.5 parts by mass of single crystal alumina (D) is added 50 =3 μm, alpha phase = 98%), 447 parts by mass of monocrystalline alumina (D) 50 =10 μm, alpha phase = 98%) was ball-milled at 600 rpm for 30 minutes, and 14.9 parts by mass of spherical boron nitride (D) was added 50 =25 μm) and 819.5 parts by mass of spherical aluminum nitride (D) surface-treated with a nonpolar silane coupling agent and an epoxy group-containing silane coupling agent in this order 50 =30 μm, breakage = 0.8%), followed by high-speed stirring, low-speed stirring, defoaming, and filtering to obtain an epoxy resin composition glue solution.
Example 7
Example 7 differs from example 1 in the D of spherical boron nitride 50 50 μm, D of spherical aluminum nitride 50 Is 90 μm.
Example 8
Example 8 differs from example 1 in the D of spherical boron nitride 50 D of spherical aluminum nitride of 15 μm 50 And was 15 μm.
Example 9
Example 9 differs from example 5 in that the spherical aluminum nitride is modified with a single nonpolar alkylsilane.
Example 10
Example 10 differs from example 5 in that the spherical aluminum nitride is modified with a single polar aminosilane.
Example 11
Example 11 differs from example 1 in that 660 parts by mass of ordinary alumina (D) was used 50 =10 μm, alpha phase = 90%) instead of 82.5 parts by mass of single crystal alumina (D) 50 =0.8 μm, alpha phase = 98.5%) and 577.5 parts by mass of a single crystal alumina (D) 50 =10 μm, α phase = 98%).
Comparative example 1
Comparative example 1 is different from example 1 in that 30 parts by mass of a dimer acid-modified bisphenol-type epoxy resin is used instead of 30 parts by mass of a bisphenol F-type epoxy resin.
Comparative example 2
Comparative example 2 differs from example 1 in that 30 parts by mass of dimer acid-modified bisphenol type epoxy resin was used instead of 15 parts by mass of biphenyl type epoxy resin and 15 parts by mass of crystalline type epoxy resin.
Comparative example 3
Comparative example 3 differs from example 3 in that the spherical boron nitride is 45.6 parts by mass.
Comparative example 4
Comparative example 4 is different from example 3 in that the spherical aluminum nitride is 684 parts by mass.
Comparative example 5
Comparative example 5 differs from example 2 in that no nanodiamond was used.
Comparative example 6
Comparative example 6 is different from example 2 in that the nanodiamond was 3.725 parts by mass.
Comparative example 7
Comparative example 7 is different from example 3 in that a fine powder mother liquor was not prepared, and nanodiamond and single crystal alumina were directly mixed with a mixed size and ball-milled.
Comparative example 8
Comparative example 8 differs from example 3 in that the nanodiamond, single crystal alumina, spherical boron nitride, spherical aluminum nitride were directly mixed with the mixed size.
The epoxy resin composition cements prepared in examples 1 to 11 and comparative examples 1 to 8 were tested, and the results are shown in Table 1. The relevant test methods are as follows:
number of powder aggregates: encapsulating, grinding and polishing the glue solution, observing the glue solution by 1000 times under a scanning electron microscope, and recording the powder agglomeration amount;
large particle breakage rate: and (3) encapsulating, grinding and polishing the glue solution, and observing the glue solution by 1000 times under a scanning electron microscope, wherein the breaking rate of large particles = the total number of broken large particles/the total number of large particles in a scanning range.
TABLE 1
As can be seen from Table 1, the epoxy resin composition glue solution prepared by the invention has ideal powder agglomeration and large particle breakage rate even under the condition of containing high-quality parts of heat-conducting powder. While comparative example 7 and comparative example 8 did not adopt the preparation process of the present invention, resulting in powder agglomeration and high crushed material of large particle powder.
Application examples
The epoxy resin composition glue solutions prepared in examples 1 to 11 were coated with a heat conductive glue layer on a release film using a comma doctor blade, and then allowed to stand and baked to remove the solvent, thereby obtaining 150 μm adhesive film samples 1 to 11.
Comparative application
And coating the epoxy resin composition glue solution prepared in the comparative examples 1 to 8 on a release film by using a comma scraper, standing, and baking to remove the solvent to obtain adhesive film samples 12 to 19 with the thickness of 150 micrometers.
Samples 1-19 were tested and the results are shown in Table 2. Wherein, the heat conductivity coefficient: testing according to ASTM D5470 Standard method; peel strength: testing according to IPC-TM-650.4.8 standard method; breakdown voltage: the test was carried out according to IPC-TM-650.2.5.6 standard method.
TABLE 2
As can be seen from Table 2, the adhesive film prepared from the epoxy resin composition glue solution of the present invention has high thermal conductivity, good fluidity, high peel strength and excellent electrical insulation property.
Compared with the sample 1, the amount of the low-viscosity resin in the sample 12 is less, the wettability of the resin system is insufficient, the fluidity, the peel strength and the breakdown voltage are all reduced, and air bubbles may exist during pressing to influence the heat conductivity coefficient; sample 13 had a small amount of crystalline resin, increased melt viscosity, and did not flow easily at high temperature, resulting in a decrease in fluidity, and the thermal conductivity, peel strength, and breakdown voltage were all affected and decreased.
Compared with the sample 3, the sample 14 has a large dosage of spherical boron nitride, and due to the large oil absorption rate of the boron nitride, the resin is adsorbed on the surface of the filler and cannot flow, and an ordered heat conduction channel cannot be formed, so that the fluidity and the heat conductivity coefficient of the bonding film are greatly reduced, and the peel strength and the breakdown voltage are also greatly reduced under the influence; in sample 15, the amount of aluminum nitride is small, and the mass fraction of the heat conductive filler is reduced, resulting in a decrease in the heat conductivity.
Compared with the sample 2, the sample 16 is not added with the nanometer heat conducting powder, the influence of the fluidity, the peeling strength and the breakdown voltage is not obvious, but the heat conducting coefficient is obviously reduced; the amount of the nano heat conductive powder in the sample 17 is too much, the resin cannot flow due to the large oil absorption rate of the nano heat conductive powder, and the adhesive film has no fluidity, so that the wettability of the resin is insufficient in the pressing process, and gaps exist, so that the heat conductivity coefficient, the peel strength and the breakdown voltage are reduced.
Compared with the preparation process of the sample 3, the sample 18 is not prepared with fine powder mother liquor, the small-particle-size powder is agglomerated to form large particles, the fluidity, the heat conductivity coefficient and the peeling strength are increased, but the breakdown voltage is very low because the powder is agglomerated to form gaps in the plate; the filler in the sample 19 is not dispersed according to particle size grading, the powder agglomeration phenomenon exists, the increase of the breakage rate causes the increase of the oil absorption rate of the filler, the decrease of the resin fluidity, and the great decrease of the thermal conductivity, the peel strength and the breakdown voltage.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent should be subject to the appended claims.
Claims (11)
1. The epoxy resin composition glue solution is characterized by comprising an epoxy resin composition and a solvent, wherein the epoxy resin composition comprises heat-conducting powder, epoxy resin and a curing agent, and the mass fraction of the heat-conducting powder in the epoxy resin composition is greater than or equal to 90%;
the heat conducting powder comprises aluminum oxide, boron nitride, aluminum nitride and nano heat conducting powder with the heat conducting coefficient larger than or equal to 500W/m.K, and the mass ratio of the nano heat conducting powder, the boron nitride, the aluminum nitride and the aluminum oxide is (0.5-2): 5-20): 550-750): 400-600;
the epoxy resin comprises 40-65 wt% of first epoxy resin and 35-60 wt% of second epoxy resin, wherein the first epoxy resin is selected from epoxy resin with the viscosity of less than or equal to 5000cps in a non-solvent type state at 25 ℃, the second epoxy resin comprises crystalline epoxy resin and biphenyl type epoxy resin, and the structural formula of the crystalline epoxy resin is shown in the specification
2. The epoxy resin composition glue solution of claim 1, wherein D of the nano heat-conducting powder is D 50 Is 8nm-200nm;
and/or D of the alumina 50 Is 0.1 μm to 40 μm;
and/or D of said boron nitride 50 20-65 μm;
and/or D of said aluminum nitride 50 Is 30-80 μm.
3. The epoxy resin composition glue solution according to claim 1, wherein the nano heat conductive powder is selected from nano diamond;
and/or the alumina is selected from single crystal alumina, and the alpha phase of the single crystal alumina is greater than or equal to 98%;
and/or the boron nitride is selected from spherical boron nitride;
and/or the aluminum nitride is selected from spherical aluminum nitride, and the spherical aluminum nitride is treated by a silane coupling agent, wherein the silane coupling agent at least comprises a nonpolar silane coupling agent and a silane coupling agent containing an epoxy group, and the carbon atom number of alkyl in the nonpolar silane coupling agent is selected from 1-12.
4. The epoxy resin composition glue solution of claim 3, wherein the spherical aluminum nitride has a breakage rate of less than 1%.
5. The epoxy resin composition glue solution according to claim 1, wherein the non-solvent type liquid epoxy resin is at least one selected from bisphenol A type epoxy resin, bisphenol F type epoxy resin and acrylic modified epoxy resin.
6. The epoxy resin composition glue solution according to claim 1, wherein the mass ratio of the crystalline epoxy resin to the biphenyl epoxy resin is 0.25.
7. The epoxy resin composition glue solution according to claim 1, wherein the curing agent at least comprises biphenyl type phenolic resin, and the mass fraction of the biphenyl type phenolic resin in the curing agent is more than 50%.
8. A method for preparing the epoxy resin composition glue solution according to any one of claims 1 to 7, characterized by comprising the following steps:
mixing heat-conducting powder with the particle size of less than or equal to 1 mu m, part of first epoxy resin and part of solvent for primary ball milling to obtain fine powder mother liquor;
mixing the rest of the first epoxy resin, the rest of the second epoxy resin, the rest of the curing agent and the rest of the solvent to obtain a mixed sizing material; and
mixing the heat-conducting powder with the grain diameter of more than 1 mu m and less than 20 mu m, the fine powder mother liquor and the mixed sizing material, performing secondary ball milling, and mixing with the heat-conducting powder with the grain diameter of more than or equal to 20 mu m to obtain the glue solution of the epoxy resin composition.
9. The preparation method of the epoxy resin composition glue solution according to claim 8, wherein the amount of the partial first epoxy resin accounts for 10-20% of the total mass of the first epoxy resin in the epoxy resin composition glue solution.
10. An adhesive film prepared from the epoxy resin composition glue solution according to any one of claims 1 to 7.
11. An adhesive film according to claim 10 for use in the preparation of a heat-dissipating metal substrate.
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| CN116445115A (en) * | 2023-04-20 | 2023-07-18 | 广东省固特尔新材料有限公司 | Low-density high-heat-conductivity pouring sealant and processing technology thereof |
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| CN114672268A (en) * | 2020-12-24 | 2022-06-28 | 广东生益科技股份有限公司 | Resin composition and application thereof |
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| 周文英等: "《聚合物基导热复合材料》", 国防工业出版社, pages: 174 - 175 * |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116445115A (en) * | 2023-04-20 | 2023-07-18 | 广东省固特尔新材料有限公司 | Low-density high-heat-conductivity pouring sealant and processing technology thereof |
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