CN114393891B - High-heat-conductivity copper-clad plate and preparation method thereof - Google Patents
High-heat-conductivity copper-clad plate and preparation method thereof Download PDFInfo
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- CN114393891B CN114393891B CN202210237469.1A CN202210237469A CN114393891B CN 114393891 B CN114393891 B CN 114393891B CN 202210237469 A CN202210237469 A CN 202210237469A CN 114393891 B CN114393891 B CN 114393891B
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- 238000002360 preparation method Methods 0.000 title claims abstract description 38
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims abstract description 98
- 229910052581 Si3N4 Inorganic materials 0.000 claims abstract description 97
- 238000003756 stirring Methods 0.000 claims abstract description 45
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000012790 adhesive layer Substances 0.000 claims abstract description 43
- 229910052802 copper Inorganic materials 0.000 claims abstract description 42
- 239000010949 copper Substances 0.000 claims abstract description 42
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 37
- 238000001035 drying Methods 0.000 claims abstract description 31
- 239000010410 layer Substances 0.000 claims abstract description 31
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 27
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000000084 colloidal system Substances 0.000 claims abstract description 24
- 229920001721 polyimide Polymers 0.000 claims abstract description 15
- 239000011248 coating agent Substances 0.000 claims abstract description 13
- 238000000576 coating method Methods 0.000 claims abstract description 13
- 239000009719 polyimide resin Substances 0.000 claims abstract description 13
- 239000002131 composite material Substances 0.000 claims abstract description 12
- 238000005498 polishing Methods 0.000 claims abstract description 12
- 239000011180 sandwich-structured composite Substances 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims description 43
- 239000003094 microcapsule Substances 0.000 claims description 30
- 238000010438 heat treatment Methods 0.000 claims description 29
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 26
- 238000005245 sintering Methods 0.000 claims description 25
- 239000000243 solution Substances 0.000 claims description 21
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 20
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 20
- 239000000843 powder Substances 0.000 claims description 20
- 239000002244 precipitate Substances 0.000 claims description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 239000000839 emulsion Substances 0.000 claims description 16
- 239000002243 precursor Substances 0.000 claims description 16
- ICSNLGPSRYBMBD-UHFFFAOYSA-N 2-aminopyridine Chemical compound NC1=CC=CC=N1 ICSNLGPSRYBMBD-UHFFFAOYSA-N 0.000 claims description 15
- 229910021389 graphene Inorganic materials 0.000 claims description 14
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 12
- 230000003746 surface roughness Effects 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 10
- LRDFRRGEGBBSRN-UHFFFAOYSA-N isobutyronitrile Chemical compound CC(C)C#N LRDFRRGEGBBSRN-UHFFFAOYSA-N 0.000 claims description 10
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 10
- 238000007873 sieving Methods 0.000 claims description 10
- MYWOJODOMFBVCB-UHFFFAOYSA-N 1,2,6-trimethylphenanthrene Chemical compound CC1=CC=C2C3=CC(C)=CC=C3C=CC2=C1C MYWOJODOMFBVCB-UHFFFAOYSA-N 0.000 claims description 9
- YYJWBYNQJLBIGS-SNAWJCMRSA-N Methyl tiglate Chemical compound COC(=O)C(\C)=C\C YYJWBYNQJLBIGS-SNAWJCMRSA-N 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 7
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 7
- 229910000077 silane Inorganic materials 0.000 claims description 7
- 235000010413 sodium alginate Nutrition 0.000 claims description 7
- 229940005550 sodium alginate Drugs 0.000 claims description 7
- 239000000661 sodium alginate Substances 0.000 claims description 7
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 7
- 229920002554 vinyl polymer Polymers 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 238000009210 therapy by ultrasound Methods 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 3
- 230000015556 catabolic process Effects 0.000 abstract description 11
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- 239000003292 glue Substances 0.000 description 10
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- 150000001335 aliphatic alkanes Chemical class 0.000 description 6
- 238000009792 diffusion process Methods 0.000 description 6
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- 239000012071 phase Substances 0.000 description 6
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- 230000009286 beneficial effect Effects 0.000 description 5
- 230000002708 enhancing effect Effects 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000001803 electron scattering Methods 0.000 description 4
- 238000004146 energy storage Methods 0.000 description 4
- 238000009413 insulation Methods 0.000 description 4
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- 239000002245 particle Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000011343 solid material Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
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- 238000005336 cracking Methods 0.000 description 2
- 230000003111 delayed effect Effects 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 230000005489 elastic deformation Effects 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- -1 polytetrafluoroethylene Polymers 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000001226 reprecipitation Methods 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- UIERETOOQGIECD-ARJAWSKDSA-M 2-Methyl-2-butenoic acid Natural products C\C=C(\C)C([O-])=O UIERETOOQGIECD-ARJAWSKDSA-M 0.000 description 1
- 229910001008 7075 aluminium alloy Inorganic materials 0.000 description 1
- UIERETOOQGIECD-UHFFFAOYSA-N Angelic acid Natural products CC=C(C)C(O)=O UIERETOOQGIECD-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Chemical group 0.000 description 1
- KNSXNCFKSZZHEA-UHFFFAOYSA-N [3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C KNSXNCFKSZZHEA-UHFFFAOYSA-N 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- DUEPRVBVGDRKAG-UHFFFAOYSA-N carbofuran Chemical compound CNC(=O)OC1=CC=CC2=C1OC(C)(C)C2 DUEPRVBVGDRKAG-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 238000007719 peel strength test Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920013636 polyphenyl ether polymer Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000010959 steel Chemical group 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- UAXOELSVPTZZQG-UHFFFAOYSA-N tiglic acid Natural products CC(C)=C(C)C(O)=O UAXOELSVPTZZQG-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
- B32B15/017—Layered products comprising a layer of metal all layers being exclusively metallic one layer being formed of aluminium or an aluminium alloy, another layer being formed of an alloy based on a non ferrous metal other than aluminium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
- B32B37/1284—Application of adhesive
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B38/00—Ancillary operations in connection with laminating processes
- B32B38/0012—Mechanical treatment, e.g. roughening, deforming, stretching
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B38/00—Ancillary operations in connection with laminating processes
- B32B38/16—Drying; Softening; Cleaning
- B32B38/164—Drying
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
-
- 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
- C09J179/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09J161/00 - C09J177/00
- C09J179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C09J179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- 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
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/302—Conductive
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2457/00—Electrical equipment
- B32B2457/08—PCBs, i.e. printed circuit boards
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Cooling Or The Like Of Semiconductors Or Solid State Devices (AREA)
- Ceramic Products (AREA)
Abstract
The application discloses a preparation method of a high-heat-conductivity copper-clad plate, which comprises the following steps: stirring polyimide resin, micro-encapsulated silicon nitride, modified graphene and acetone to obtain a heat-conducting colloid; polishing and coarsening a plane of each of the copper plate and the aluminum plate; and uniformly coating the heat-conducting colloid on the polished and roughened plane of the aluminum plate to form a heat-conducting adhesive layer, attaching the polished and roughened plane of the copper plate to the heat-conducting adhesive layer to obtain a three-layer sandwich-structured composite plate, and drying the composite plate to obtain the high-heat-conducting copper-clad plate. The high-heat-conductivity copper-clad plate has good heat conductivity and higher breakdown voltage.
Description
Technical Field
The application relates to the technical field of heat conduction materials, in particular to a high-heat conduction copper-clad plate and a preparation method thereof.
Background
With the development of microelectronic integration technology, the volumes of electronic components and logic circuits are reduced by tens of thousands of times, and in order to ensure the normal operation of electronic equipment, the use of high-heat-dissipation heat-conduction materials is a key link. This requires materials that possess excellent insulation, thermo-mechanical properties, and heat conducting and dissipating functions. The copper-clad plate is prepared by coating a base material with a high polymer and then hot-pressing with a copper foil, and common high polymer materials comprise epoxy resin, polyimide, polytetrafluoroethylene, polyphenyl ether resin and the like, and have the characteristics in application, wherein the polyimide has excellent mechanical, electrical and thermal properties, good ductility and processability, and has the functions of mechanically supporting and insulating electronic circuit elements, and is widely used in the preparation of heat-conducting layers of products such as flexible copper-clad plates.
Disclosure of Invention
Aiming at the defects in the prior art, the application provides a high-heat-conductivity copper-clad plate and a preparation method thereof.
The technical scheme adopted by the application is as follows:
the preparation method of the high-heat-conductivity copper-clad plate comprises the following steps of:
mixing 25-35 parts by weight of polyimide resin, 10-20 parts by weight of micro-encapsulated silicon nitride and 70-90 parts by weight of acetone at 25-35 ℃ at 200-300rpm for 0.5-1.5 hours to obtain a heat conducting colloid; polishing and coarsening one plane of each of the copper plate and the aluminum plate, wherein the surface roughness is required to reach Ra=25-100; uniformly coating the heat-conducting colloid on the polished and roughened plane of the aluminum plate to form a heat-conducting adhesive layer, and then attaching the polished and roughened plane of the copper plate to the heat-conducting adhesive layer to obtain the three-layer sandwich-structured composite plate; drying the composite board at 230-250 ℃ for 1-3 hours to obtain the high-heat-conductivity copper-clad plate; the thickness of the copper plate is 25-35 mu m, the thickness of the aluminum plate is 0.8-1.2mm, and the thickness of the heat conducting glue layer is 22-28 mu m.
Preferably, the preparation method of the high-heat-conductivity copper-clad plate comprises the following steps of: mixing 25-35 parts by weight of polyimide resin, 10-20 parts by weight of microcapsule silicon nitride, 1-5 parts by weight of modified graphene and 70-90 parts by weight of acetone at a temperature of 25-35 ℃ at 200-300rpm for 0.5-1.5 hours to obtain a heat conducting colloid; polishing and coarsening one plane of each of the copper plate and the aluminum plate, wherein the surface roughness is required to reach Ra=25-100; uniformly coating the heat-conducting colloid on the polished and roughened plane of the aluminum plate to form a heat-conducting adhesive layer, and then attaching the polished and roughened plane of the copper plate to the heat-conducting adhesive layer to obtain the three-layer sandwich-structured composite plate; drying the composite board at 230-250 ℃ for 1-3 hours to obtain the high-heat-conductivity copper-clad plate; the thickness of the copper plate is 25-35 mu m, the thickness of the aluminum plate is 0.8-1.2mm, and the thickness of the heat conducting glue layer is 22-28 mu m.
The preparation method of the modified graphene comprises the following steps:
adding graphene and 2-aminopyridine into an ethanol water solution with the weight percent of 50-65%, and performing ultrasonic treatment for 20-50min under the conditions of 20-30kHz and 200-300W, wherein the mass ratio of the graphene to the 2-aminopyridine to ethanol water solution is (6-12) (0.1-0.5): 50; adding vinyl tributyl ketoxime silane, sodium alginate and aluminum chloride, and continuing ultrasonic treatment for 50-100min, wherein the mass ratio of the vinyl tributyl ketoxime silane, the sodium alginate, the aluminum chloride and the graphene is (0.1-0.3): 1-2): 1-3): 10, so as to obtain a mixed solution I; dripping 30-50wt% sodium hydroxide aqueous solution into the mixed solution I at the temperature of 70-80 ℃ and at the speed of 100-200rpm at the speed of 1-3mL/min, and continuously stirring for 100-150min after the dripping is finished, wherein the mass ratio of the sodium hydroxide aqueous solution to the graphene is 1 (1-5); centrifuging, taking the precipitate, drying and grinding to obtain the modified graphene.
The preparation method of the microcapsule silicon nitride comprises the following steps: mixing heat-conducting silicon nitride and KH570 silane coupling agent according to the mass ratio of (0.8-1.2), and dispersing for 1.5-2.5h by using ultrasonic waves with the power of 500-700w and the frequency of 30-40 kHz; then adding 60-67% ethanol water solution by mass percent, wherein the mass ratio of the heat-conducting silicon nitride to the KH570 silane coupling agent to the ethanol water solution is (0.8-1.2) (4.5-5.5), and stirring at 160-200rpm for 3h at 75-85 ℃; drying at 125-135 deg.c for 0.5-2 hr to obtain precursor; mixing the precursor, n-hexadecane, pentaerythritol tetraacrylate, methyl tiglate and deionized water according to the mass ratio of (0.8-1.2), (18-22), (5-10), (12-17), (25-35), dispersing for 0.5-2h by using ultrasonic waves with the power of 500-700w and the frequency of 30-40kHz, and stirring at 300-400rpm for 0.5-2h at 35-45 ℃ to obtain emulsion; mixing the emulsion and isobutyronitrile according to the mass ratio of (8-12) (0.8-12), stirring at the temperature of 70-80 ℃ for 12 hours at the speed of 540-660rpm, centrifuging at the speed of 1200rpm for 12 minutes to obtain a precipitate, and drying the precipitate at the temperature of 65 ℃ for 12 hours to obtain the microcapsule silicon nitride.
In silicon nitride, beta-Si in the form of large-size long rod 3 N 4 The number of various lattice defects and grain boundaries can be obviously reduced in the nucleation and growth processes of the crystal grains; heat in solid materialThe conduction of (2) depends on lattice vibration, namely phonon diffusion, and lattice defects and crystal boundaries can generate scattering effect on phonons, namely heat conduction is prevented; and, the thermal conductivity of the glass phase at the grain boundary is very low, and the reduction of the number of the grain boundary means that the thermal conductivity of the whole silicon nitride is increased; ceO (CeO) 2 Has very remarkable promotion effect on grain rearrangement in the sintering process of silicon nitride, so CeO is added in the sintering process of the silicon nitride 2 Silicon nitride with higher relative density can be obtained; yb 2 O 3 Can increase the average grain size of silicon nitride and increase the content of fine grains, thereby adding CeO 2 And Yb 2 O 3 The grain size, morphology, density and microstructure of the obtained heat-conducting silicon nitride can be regulated and controlled by compounding, so that the heat-conducting adhesive layer with higher heat conductivity coefficient is obtained. The propagation of electric field in solid material is affected by crystal defects such as crystal boundary, dislocation, lattice distortion, etc., and various crystal defects can produce scattered waves with different phases and different intensities for electrons, and the application adopts CeO 2 And Yb 2 O 3 The concentration of crystal defects of the obtained heat-conducting silicon nitride crystal system can be effectively regulated and controlled by compounding, so that superposition of electron scattering waves is enhanced, the volume resistance in the whole material system is increased, the heat conductivity of the material is increased, and meanwhile, the insulation performance is enhanced, and therefore, the breakdown voltage is also increased. When the material is deformed, inherent crystal defects contained in the material can absorb deformation energy, so that damage to the material caused by deformation is delayed to a certain extent; the application adopts CeO 2 And Yb 2 O 3 The compound can effectively regulate and control the concentration of crystal defects of the obtained heat-conducting silicon nitride crystal system, thereby enhancing the deformation energy received by the heat-conducting adhesive layer when the heat-conducting adhesive layer is peeled, and further improving the peeling resistance of the material.
The second order sintering helps to prolong the dissolution/re-precipitation process in liquid phase sintering, because the process provides diffusion power and time for the rearrangement of atoms and avoids cracking caused by lattice diffusion mismatch due to direct temperature reaching 1850 ℃, thus being beneficial to the alpha-Si 3 N 4 Conversion to beta-Si 3 N 4 Phase transformation of (C) occurs while also promoting beta-Si of large-sized long rod shape and having higher thermal conductivity 3 N 4 Nucleation and growth of (3). CeO is added with 2 And Yb 2 O 3 The grain size, morphology, density and microstructure of the obtained heat-conducting silicon nitride can be regulated and controlled by compounding, so that the heat-conducting adhesive layer with higher heat conductivity coefficient is obtained. The application adopts CeO 2 And Yb 2 O 3 The concentration of crystal defects of the obtained heat-conducting silicon nitride crystal system can be effectively regulated and controlled by compounding, so that superposition of electron scattering waves is enhanced, the volume resistance in the whole material system is increased, the heat conductivity of the material is increased, and meanwhile, the insulation performance is enhanced, and therefore, the breakdown voltage is also increased. The application adopts CeO 2 And Yb 2 O 3 The compound can effectively regulate and control the concentration of crystal defects of the obtained heat-conducting silicon nitride crystal system, thereby enhancing the deformation energy received by the heat-conducting adhesive layer when the heat-conducting adhesive layer is peeled, and further improving the peeling resistance of the material.
The microcapsule silicon nitride is prepared by taking n-hexadecane as a wrapping shell to establish a net structure, so that the specific surface area of the silicon nitride in a heat conducting adhesive layer is increased, and the heat exchange area is increased; the microcapsule has certain elasticity due to the alkane long chain of hexadecane, so that the microcapsule has stability against volume expansion and contraction when the temperature changes, and improves the heat conduction efficiency and the thermal cycle stability and heat resistance; the microcapsule silicon nitride prepared by the method has strong heat energy storage density and short heat response time due to the spherical wrapping structure, and is further beneficial to heat transfer. KH570 silane coupling agents increase the number of branches attached to n-hexadecane, the presence of these branches increasing the energy storage density. The alkane wrapping layer of the outer layer of the microcapsule silicon nitride prepared by the specific method has certain insulating property, so that the breakdown voltage of the material can be increased. The microcapsule silicon nitride prepared by the specific method has the advantages that the alkane wrapping layer with certain elasticity on the outer layer can provide elastic deformation within a certain safety range when the adhesive layer is subjected to tensile force, and can obviously absorb energy so as to keep the whole adhesive layer in an energy steady state without breaking.
The preparation method of the heat-conducting silicon nitride comprises the following steps: by reacting alpha-Si 3 N 4 Mixing with sintering aid (95-105) (1.2-1.8) and stirring at 60-150rpm for 0.5-1.5h to obtain prefabricated powder; heating the prefabricated powder at a heating rate of 1-2.5 ℃/min under nitrogen atmosphere, preserving heat for 1.5-2.5h when the temperature reaches 1550-1650 ℃, then continuing to heat at a heating rate of 1-2.5 ℃/min, preserving heat for 1.5-2.5h when the temperature reaches 1800-1900 ℃, cooling along with a furnace, and sieving with a 800-1200 mesh sieve after crushing to obtain the heat-conducting silicon nitride.
The sintering aid is CeO 2 、Yb 2 O 3 One or a mixture of both. Preferably, the sintering aid is CeO 2 、Yb 2 O 3 The mixture is prepared from (1-3) and (1-3) according to the mass ratio.
The high-heat-conductivity copper-clad plate is prepared by adopting the method.
The application has the beneficial effects that: the high-heat-conductivity copper-clad plate has good heat conductivity, higher breakdown voltage and peeling strength, simple and convenient manufacturing process and convenient production and application.
Detailed Description
The above summary of the present application is described in further detail below in conjunction with the detailed description, but it should not be understood that the scope of the above-described subject matter of the present application is limited to the following examples.
Introduction of partial raw materials in the application:
copper plate, CAS:7440-50-8 available from Huahu iron and Steel group Co., ltd., brand: mitsubishi, japan, brand: c1100, copper content is more than or equal to 99.9%, thickness is 30 μm, and the requirements of GB/T2059-2017 are met.
Aluminum plate, CAS:7429-90-5, available from Kunshan Torpedo aluminum, inc., trade mark: the 7075 aluminum alloy has the thickness of 1mm and meets the requirements of GB/T3190-2008.
Polyimide resin, CAS:26023-21-2, available from Dongguan square scale plastics Inc., brand: SAIBC, level: high-grade pure GR, brand: XH10158.
Acetone, CAS:67-64-1, commercially available from Nanjing chemical agents Co., ltd., product number: C0720114023.
KH570 silane coupling agent, CAS:2530-85-0, commercially available from Nanjing chemical reagents, inc., under the trade designation: C0573600019.
pentaerythritol tetraacrylate, CAS:4986-89-4 available from western asia chemical technology (shandong) limited under order number: a32038-500G.
Tiglic acid methyl ester, CAS:6622-76-0 available from carbofuran technologies, inc., product number: t0248.
Isobutyronitrile, CAS:78-82-0, available from Hubei Universal medicine Co., ltd.
α-Si 3 N 4 CAS:12033-89-5, available from Siya chemical technology (Shandong) Inc., order number: d18579-250g, particle size: 80nm, and the purity is more than or equal to 99.9 percent.
CeO 2 CAS:1306-38-3 available from western asia chemical technology (shandong) inc, order number: a30788-100g, particle size: 85nm, and the purity is more than or equal to 99.9 percent.
Yb 2 O 3 CAS:1314-37-0, available from western asia chemical technology (shandong) limited, order number: a10010-100g, particle diameter: 85nm, and the purity is more than or equal to 99.9 percent.
Graphene, CAS:1034343-98-0, thickness 4-7nm, diap.). 6*6 μm from Ai Lan (Shanghai) chemical technology Co., ltd.
Vinyl tributylketoxime silane, CAS:2224-33-1, available from Hubei Korea chemical Co., ltd.
2-aminopyridine, CAS:504-29-0 available from Shanghai dry stiffness engineering Co., ltd.
Sodium alginate, CAS:9005-38-3, viscosity 200mpa.s (25 ℃ C.), available from chemical industry Co., ltd. In Beijing Hua Weirui.
Example 1
The preparation method of the high-heat-conductivity copper-clad plate comprises the following steps of:
mixing 30 parts by weight of polyimide resin, 15 parts by weight of microencapsulated silicon nitride and 80 parts by weight of acetone, and stirring at 240rpm at 30 ℃ for 1 hour to obtain a heat-conducting colloid; polishing and coarsening one plane of each of the copper plate and the aluminum plate, wherein the surface roughness is required to reach Ra=50; uniformly coating the heat-conducting colloid on the polished and roughened plane of the aluminum plate to form a heat-conducting adhesive layer, and then attaching the polished and roughened plane of the copper plate to the heat-conducting adhesive layer to obtain the three-layer sandwich-structured composite plate; and drying the composite board for 2 hours at 240 ℃ to obtain the high-heat-conductivity copper-clad plate. The thickness of the copper plate is 30 mu m, the thickness of the aluminum plate is 1mm, and the thickness of the heat conducting glue layer is 25 mu m.
The preparation method of the microcapsule silicon nitride comprises the following steps:
mixing heat-conducting silicon nitride and KH570 silane coupling agent according to a mass ratio of 1:1, and dispersing for 2h by using ultrasonic waves with power of 600w and frequency of 35 kHz; then adding 65% ethanol water solution by mass, wherein the mass ratio of the heat-conducting silicon nitride to the KH570 silane coupling agent to the ethanol water solution is 1:1:5, and stirring at 180rpm for 3 hours at 80 ℃; subsequently drying at 130 ℃ for 1h to obtain a precursor; mixing the precursor, n-hexadecane, pentaerythritol tetraacrylate, methyl tiglate and deionized water according to a mass ratio of 1:20:8:15:30, dispersing for 1h by using ultrasonic waves with power of 600w and frequency of 35kHz, and stirring for 1h at 360rpm at 40 ℃ to obtain emulsion; mixing the emulsion and isobutyronitrile according to a mass ratio of 10:1, stirring at 600rpm for 12 hours at 75 ℃, centrifuging at 1200rpm for 12 minutes to obtain a precipitate, and drying the precipitate at 65 ℃ for 12 hours to obtain the microcapsule silicon nitride.
The preparation method of the heat-conducting silicon nitride comprises the following steps: by reacting alpha-Si 3 N 4 Mixing with sintering aid according to the mass ratio of 100:1.5, and stirring at 120rpm for 1h to obtain prefabricated powder; the sintering aid is CeO 2 、Yb 2 O 3 A mixture according to a mass ratio of 1:1; heating the prefabricated powder at a heating rate of 2 ℃/min under nitrogen atmosphere, preserving heat for 2 hours when the temperature reaches 1600 ℃, then continuing to heat at the heating rate of 2 ℃/min, preserving heat for 2 hours when the temperature reaches 1850 ℃, cooling along with a furnace, crushing, and sieving with a 1000-mesh sieve to obtain the heat-conducting silicon nitride.
Example 2
Substantially the same as in example 1, the only difference is that: the preparation method of the microcapsule silicon nitride comprises the following steps:
mixing heat-conducting silicon nitride and KH570 silane coupling agent according to a mass ratio of 1:1, and dispersing for 2h by using ultrasonic waves with power of 600w and frequency of 35 kHz; then adding 65% ethanol water solution by mass, wherein the mass ratio of the heat-conducting silicon nitride to the KH570 silane coupling agent to the ethanol water solution is 1:1:5, and stirring at 180rpm for 3 hours at 80 ℃; subsequently drying at 130 ℃ for 1h to obtain a precursor; mixing the precursor, n-hexadecane, pentaerythritol tetraacrylate, methyl tiglate and deionized water according to a mass ratio of 1:20:8:15:30, dispersing for 1h by using ultrasonic waves with power of 600w and frequency of 35kHz, and stirring for 1h at 360rpm at 40 ℃ to obtain emulsion; mixing the emulsion and isobutyronitrile according to a mass ratio of 10:1, stirring at 600rpm for 12 hours at 75 ℃, centrifuging at 1200rpm for 12 minutes to obtain a precipitate, and drying the precipitate at 65 ℃ for 12 hours to obtain the microcapsule silicon nitride.
The preparation method of the heat-conducting silicon nitride comprises the following steps: by reacting alpha-Si 3 N 4 Mixing with sintering aid according to the mass ratio of 100:1.5, and stirring at 120rpm for 1h to obtain prefabricated powder; the sintering aid is CeO 2 The method comprises the steps of carrying out a first treatment on the surface of the Heating the prefabricated powder at a heating rate of 2 ℃/min under nitrogen atmosphere, preserving heat for 2 hours when the temperature reaches 1600 ℃, then continuing to heat at the heating rate of 2 ℃/min, preserving heat for 2 hours when the temperature reaches 1850 ℃, cooling along with a furnace, crushing, and sieving with a 1000-mesh sieve to obtain the heat-conducting silicon nitride.
Example 3
Substantially the same as in example 1, the only difference is that: the preparation method of the microcapsule silicon nitride comprises the following steps:
mixing heat-conducting silicon nitride and KH570 silane coupling agent according to a mass ratio of 1:1, and dispersing for 2h by using ultrasonic waves with power of 600w and frequency of 35 kHz; then adding 65% ethanol water solution by mass, wherein the mass ratio of the heat-conducting silicon nitride to the KH570 silane coupling agent to the ethanol water solution is 1:1:5, and stirring at 180rpm for 3 hours at 80 ℃; subsequently drying at 130 ℃ for 1h to obtain a precursor; mixing the precursor, n-hexadecane, pentaerythritol tetraacrylate, methyl tiglate and deionized water according to a mass ratio of 1:20:8:15:30, dispersing for 1h by using ultrasonic waves with power of 600w and frequency of 35kHz, and stirring for 1h at 360rpm at 40 ℃ to obtain emulsion; mixing the emulsion and isobutyronitrile according to a mass ratio of 10:1, stirring at 600rpm for 12 hours at 75 ℃, centrifuging at 1200rpm for 12 minutes to obtain a precipitate, and drying the precipitate at 65 ℃ for 12 hours to obtain the microcapsule silicon nitride.
The preparation method of the heat-conducting silicon nitride comprises the following steps: by reacting alpha-Si 3 N 4 Mixing with sintering aid according to the mass ratio of 100:1.5, and stirring at 120rpm for 1h to obtain prefabricated powder; the sintering aid is Yb 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the Heating the prefabricated powder at a heating rate of 2 ℃/min under nitrogen atmosphere, preserving heat for 2 hours when the temperature reaches 1600 ℃, then continuing to heat at the heating rate of 2 ℃/min, preserving heat for 2 hours when the temperature reaches 1850 ℃, cooling along with a furnace, crushing, and sieving with a 1000-mesh sieve to obtain the heat-conducting silicon nitride.
Comparative example 1
The preparation method of the high-heat-conductivity copper-clad plate comprises the following steps of:
30 parts by weight of polyimide resin, 15 parts by weight of alpha-Si 3 N 4 Mixing 80 parts by weight of acetone, and stirring at 240rpm for 1h at 30 ℃ to obtain a heat-conducting colloid; polishing and coarsening one plane of each of the copper plate and the aluminum plate, wherein the surface roughness is required to reach Ra=50; uniformly coating the heat-conducting colloid on the polished and roughened plane of the aluminum plate to form a heat-conducting adhesive layer, and then attaching the polished and roughened plane of the copper plate to the heat-conducting adhesive layer to obtain the three-layer sandwich-structured composite plate; drying the composite board for 2 hours at 240 ℃ to obtain the high-heat-conductivity copper-clad plate; the thickness of the copper plate is 30 mu m, the thickness of the aluminum plate is 1mm, and the thickness of the heat conducting glue layer is 25 mu m.
Comparative example 2
The preparation method of the high-heat-conductivity copper-clad plate comprises the following steps of:
mixing 30 parts by weight of polyimide resin, 15 parts by weight of heat-conducting silicon nitride and 80 parts by weight of acetone, and stirring at 240rpm for 1 hour at 30 ℃ to obtain a heat-conducting colloid; polishing and coarsening one plane of each of the copper plate and the aluminum plate, wherein the surface roughness is required to reach Ra=50; uniformly coating the heat-conducting colloid on the polished and roughened plane of the aluminum plate to form a heat-conducting adhesive layer, and then attaching the polished and roughened plane of the copper plate to the heat-conducting adhesive layer to obtain the three-layer sandwich-structured composite plate; drying the composite board for 2 hours at 240 ℃ to obtain the high-heat-conductivity copper-clad plate; the thickness of the copper plate is 30 mu m, the thickness of the aluminum plate is 1mm, and the thickness of the heat conducting glue layer is 25 mu m.
The preparation method of the heat-conducting silicon nitride comprises the following steps: by reacting alpha-Si 3 N 4 Stirring at 120rpm for 1h to obtain prefabricated powder; heating the prefabricated powder at a heating rate of 2 ℃/min under the nitrogen atmosphere, preserving heat for 2 hours when the temperature reaches 1850 ℃, cooling along with a furnace, crushing, and sieving with a 1000-mesh sieve to obtain the heat-conducting silicon nitride.
Comparative example 3
The preparation method of the high-heat-conductivity copper-clad plate comprises the following steps of:
mixing 30 parts by weight of polyimide resin, 15 parts by weight of heat-conducting silicon nitride and 80 parts by weight of acetone, and stirring at 240rpm for 1 hour at 30 ℃ to obtain a heat-conducting colloid; polishing and coarsening one plane of each of the copper plate and the aluminum plate, wherein the surface roughness is required to reach Ra=50; uniformly coating the heat-conducting colloid on the polished and roughened plane of the aluminum plate to form a heat-conducting adhesive layer, and then attaching the polished and roughened plane of the copper plate to the heat-conducting adhesive layer to obtain the three-layer sandwich-structured composite plate; drying the composite board for 2 hours at 240 ℃ to obtain the high-heat-conductivity copper-clad plate; the thickness of the copper plate is 30 mu m, the thickness of the aluminum plate is 1mm, and the thickness of the heat conducting glue layer is 25 mu m.
The preparation method of the heat-conducting silicon nitride comprises the following steps: by reacting alpha-Si 3 N 4 Stirring at 120rpm for 1h to obtain prefabricated powder; heating the prefabricated powder at a heating rate of 2 ℃/min under nitrogen atmosphere, preserving heat for 2 hours when the temperature reaches 1600 ℃, then continuing to heat at the heating rate of 2 ℃/min, preserving heat for 2 hours when the temperature reaches 1850 ℃, cooling along with a furnace, crushing, and sieving with a 1000-mesh sieve to obtain the heat-conducting silicon nitride.
Comparative example 4
The preparation method of the high-heat-conductivity copper-clad plate comprises the following steps of:
mixing 30 parts by weight of polyimide resin, 15 parts by weight of heat-conducting silicon nitride and 80 parts by weight of acetone, and stirring at 240rpm for 1 hour at 30 ℃ to obtain a heat-conducting colloid; polishing and coarsening one plane of each of the copper plate and the aluminum plate, wherein the surface roughness is required to reach Ra=50; uniformly coating the heat-conducting colloid on the polished and roughened plane of the aluminum plate to form a heat-conducting adhesive layer, and then attaching the polished and roughened plane of the copper plate to the heat-conducting adhesive layer to obtain the three-layer sandwich-structured composite plate; drying the composite board for 2 hours at 240 ℃ to obtain the high-heat-conductivity copper-clad plate; the thickness of the copper plate is 30 mu m, the thickness of the aluminum plate is 1mm, and the thickness of the heat conducting glue layer is 25 mu m.
The preparation method of the heat-conducting silicon nitride comprises the following steps: by reacting alpha-Si 3 N 4 Mixing with sintering aid according to the mass ratio of 100:1.5, and stirring at 120rpm for 1h to obtain prefabricated powder; the sintering aid is CeO 2 The method comprises the steps of carrying out a first treatment on the surface of the Heating the prefabricated powder at a heating rate of 2 ℃/min under nitrogen atmosphere, preserving heat for 2 hours when the temperature reaches 1600 ℃, then continuing to heat at the heating rate of 2 ℃/min, preserving heat for 2 hours when the temperature reaches 1850 ℃, cooling along with a furnace, crushing, and sieving with a 1000-mesh sieve to obtain the heat-conducting silicon nitride.
Comparative example 5
The preparation method of the high-heat-conductivity copper-clad plate comprises the following steps of:
mixing 30 parts by weight of polyimide resin, 15 parts by weight of microencapsulated silicon nitride and 80 parts by weight of acetone, and stirring at 240rpm at 30 ℃ for 1 hour to obtain a heat-conducting colloid; polishing and coarsening one plane of each of the copper plate and the aluminum plate, wherein the surface roughness is required to reach Ra=50; uniformly coating the heat-conducting colloid on the polished and roughened plane of the aluminum plate to form a heat-conducting adhesive layer, and then attaching the polished and roughened plane of the copper plate to the heat-conducting adhesive layer to obtain the three-layer sandwich-structured composite plate; drying the composite board for 2 hours at 240 ℃ to obtain the high-heat-conductivity copper-clad plate; the thickness of the copper plate is 30 mu m, the thickness of the aluminum plate is 1mm, and the thickness of the heat conducting glue layer is 25 mu m.
The preparation method of the microcapsule silicon nitride comprises the following steps: by reacting alpha-Si 3 N 4 Mixing KH570 silane coupling agent according to the mass ratio of 1:1, and dispersing for 2 hours by using ultrasonic waves with the power of 600w and the frequency of 35 kHz; then adding the massThe mass ratio of the heat-conducting silicon nitride to the KH570 silane coupling agent to the ethanol aqueous solution with the fraction of 65% is 1:1:5, and the heat-conducting silicon nitride to the KH570 silane coupling agent and the ethanol aqueous solution are stirred at 180rpm for 3 hours at 80 ℃; subsequently drying at 130 ℃ for 1h to obtain a precursor; mixing the precursor, n-hexadecane, pentaerythritol tetraacrylate, methyl tiglate and deionized water according to a mass ratio of 1:20:8:15:30, dispersing for 1h by using ultrasonic waves with power of 600w and frequency of 35kHz, and stirring for 1h at 360rpm at 40 ℃ to obtain emulsion; mixing the emulsion and isobutyronitrile according to a mass ratio of 10:1, stirring at 600rpm for 12 hours at 75 ℃, centrifuging at 1200rpm for 12 minutes to obtain a precipitate, and drying the precipitate at 65 ℃ for 12 hours to obtain the microcapsule silicon nitride.
Example 4
The preparation method of the high-heat-conductivity copper-clad plate comprises the following steps of:
mixing 30 parts by weight of polyimide resin, 15 parts by weight of microencapsulated silicon nitride, 3 parts by weight of modified graphene and 80 parts by weight of acetone, and stirring at 240rpm for 1 hour at 30 ℃ to obtain a heat-conducting colloid; polishing and coarsening one plane of each of the copper plate and the aluminum plate, wherein the surface roughness is required to reach Ra=50; uniformly coating the heat-conducting colloid on the polished and roughened plane of the aluminum plate to form a heat-conducting adhesive layer, and then attaching the polished and roughened plane of the copper plate to the heat-conducting adhesive layer to obtain the three-layer sandwich-structured composite plate; and drying the composite board for 2 hours at 240 ℃ to obtain the high-heat-conductivity copper-clad plate. The thickness of the copper plate is 30 mu m, the thickness of the aluminum plate is 1mm, and the thickness of the heat conducting glue layer is 25 mu m.
The preparation method of the modified graphene comprises the following steps:
adding graphene and 2-aminopyridine into a 60wt% ethanol water solution, and performing ultrasonic treatment for 30min under the conditions of 25kHz and 300W, wherein the mass ratio of the graphene to the 2-aminopyridine to the ethanol water solution is 10:0.3:50; adding vinyl tributyl ketoxime silane, sodium alginate and aluminum chloride, and continuing ultrasonic treatment for 60min, wherein the mass ratio of the vinyl tributyl ketoxime silane to the sodium alginate to the aluminum chloride to the graphene is 0.3:1:2:10, so as to obtain a mixed solution I; dripping 40wt% sodium hydroxide aqueous solution into the mixed solution I at the temperature of 75 ℃ and at the speed of 150rpm, and continuously stirring for 120min after the dripping is finished, wherein the mass ratio of the sodium hydroxide aqueous solution to the graphene is 1:3; centrifuging, taking the precipitate, drying and grinding to obtain the modified graphene.
The preparation method of the microcapsule silicon nitride comprises the following steps:
mixing heat-conducting silicon nitride and KH570 silane coupling agent according to a mass ratio of 1:1, and dispersing for 2h by using ultrasonic waves with power of 600w and frequency of 35 kHz; then adding 65% ethanol water solution by mass, wherein the mass ratio of the heat-conducting silicon nitride to the KH570 silane coupling agent to the ethanol water solution is 1:1:5, and stirring at 180rpm for 3 hours at 80 ℃; subsequently drying at 130 ℃ for 1h to obtain a precursor; mixing the precursor, n-hexadecane, pentaerythritol tetraacrylate, methyl tiglate and deionized water according to a mass ratio of 1:20:8:15:30, dispersing for 1h by using ultrasonic waves with power of 600w and frequency of 35kHz, and stirring for 1h at 360rpm at 40 ℃ to obtain emulsion; mixing the emulsion and isobutyronitrile according to a mass ratio of 10:1, stirring at 600rpm for 12 hours at 75 ℃, centrifuging at 1200rpm for 12 minutes to obtain a precipitate, and drying the precipitate at 65 ℃ for 12 hours to obtain the microcapsule silicon nitride.
The preparation method of the heat-conducting silicon nitride comprises the following steps: by reacting alpha-Si 3 N 4 Mixing with sintering aid according to the mass ratio of 100:1.5, and stirring at 120rpm for 1h to obtain prefabricated powder; the sintering aid is CeO 2 、Yb 2 O 3 A mixture according to a mass ratio of 1:1; heating the prefabricated powder at a heating rate of 2 ℃/min under nitrogen atmosphere, preserving heat for 2 hours when the temperature reaches 1600 ℃, then continuing to heat at the heating rate of 2 ℃/min, preserving heat for 2 hours when the temperature reaches 1850 ℃, cooling along with a furnace, crushing, and sieving with a 1000-mesh sieve to obtain the heat-conducting silicon nitride. The high heat conductive copper clad laminate of example 4 was measured by the method of test example 1 to have a heat conductivity of 3.55W/(m·k).
Comparative example 6
The preparation method of the high-heat-conductivity copper-clad plate comprises the following steps of:
mixing 30 parts by weight of polyimide resin, 15 parts by weight of microencapsulated silicon nitride, 3 parts by weight of graphene and 80 parts by weight of acetone, and stirring at 240rpm for 1 hour at 30 ℃ to obtain a heat-conducting colloid; polishing and coarsening one plane of each of the copper plate and the aluminum plate, wherein the surface roughness is required to reach Ra=50; uniformly coating the heat-conducting colloid on the polished and roughened plane of the aluminum plate to form a heat-conducting adhesive layer, and then attaching the polished and roughened plane of the copper plate to the heat-conducting adhesive layer to obtain the three-layer sandwich-structured composite plate; and drying the composite board for 2 hours at 240 ℃ to obtain the high-heat-conductivity copper-clad plate. The thickness of the copper plate is 30 mu m, the thickness of the aluminum plate is 1mm, and the thickness of the heat conducting glue layer is 25 mu m.
The preparation method of the microcapsule silicon nitride comprises the following steps:
mixing heat-conducting silicon nitride and KH570 silane coupling agent according to a mass ratio of 1:1, and dispersing for 2h by using ultrasonic waves with power of 600w and frequency of 35 kHz; then adding 65% ethanol water solution by mass, wherein the mass ratio of the heat-conducting silicon nitride to the KH570 silane coupling agent to the ethanol water solution is 1:1:5, and stirring at 180rpm for 3 hours at 80 ℃; subsequently drying at 130 ℃ for 1h to obtain a precursor; mixing the precursor, n-hexadecane, pentaerythritol tetraacrylate, methyl tiglate and deionized water according to a mass ratio of 1:20:8:15:30, dispersing for 1h by using ultrasonic waves with power of 600w and frequency of 35kHz, and stirring for 1h at 360rpm at 40 ℃ to obtain emulsion; mixing the emulsion and isobutyronitrile according to a mass ratio of 10:1, stirring at 600rpm for 12 hours at 75 ℃, centrifuging at 1200rpm for 12 minutes to obtain a precipitate, and drying the precipitate at 65 ℃ for 12 hours to obtain the microcapsule silicon nitride.
The preparation method of the heat-conducting silicon nitride comprises the following steps: by reacting alpha-Si 3 N 4 Mixing with sintering aid according to the mass ratio of 100:1.5, and stirring at 120rpm for 1h to obtain prefabricated powder; the sintering aid is CeO 2 、Yb 2 O 3 A mixture according to a mass ratio of 1:1; heating the prefabricated powder at a heating rate of 2 ℃/min under nitrogen atmosphere, preserving heat for 2 hours when the temperature reaches 1600 ℃, then continuing to heat at the heating rate of 2 ℃/min, preserving heat for 2 hours when the temperature reaches 1850 ℃, cooling along with a furnace, crushing, and sieving with a 1000-mesh sieve to obtain the heat-conducting silicon nitride. The high heat conductive copper clad laminate of comparative example 6 was measured by the method of test example 1 to have a heat conductivity of 3.03W/(m·k).
Test example 1
And (3) heat conduction coefficient test: the thermal conductivity of the high thermal conductivity copper clad laminate obtained in each of the above examples and comparative examples was measured according to GB/T22588-2008 "flash method for measuring thermal diffusivity or thermal conductivity". The test temperature is 350+/-1K; a wafer-shaped specimen having a diameter of 6mm was used, and the specimen had a thickness of 1.055mm.
Table 1 coefficient of thermal conductivity of high thermal conductivity copper clad laminate
Test example 2
Breakdown voltage test: according to GB/T1408.1-2016 section 1 of insulating Material Electrical Strength test method: test at power frequency. An electrode with the same diameter is adopted; the length of the sample is 100mm, the width is 25mm, and the thickness is 1.055mm; the test temperature was 25℃and the relative humidity was 50%.
TABLE 2 breakdown voltage of high thermal conductivity copper clad laminate
| Breakdown voltage (kV) | |
| Example 1 | 5.5 |
| Example 2 | 5.3 |
| Example 3 | 5.1 |
| Comparative example 1 | 3.2 |
| Comparative example 2 | 3.8 |
| Comparative example 3 | 4.0 |
| Comparative example 4 | 4.4 |
| Comparative example 5 | 2.7 |
Test example 3
Peel strength test: according to GB/T13557-2017 test method for flexible copper-clad materials for printed circuits. The size of the adopted sample is 200mm multiplied by 3.0mm, and the thickness is 1.055mm; the stripping rate of the tensile testing machine is 50mm/min, and the minimum resolution of the tensile reading is 0.01N; prior to testing, the samples were placed in an environment at 25 ℃ and 50% relative humidity for 24 hours; during the test, the tensile force aroma forms 90 degrees with the plane of the base material; the stripping length is 100mm; the peel strength of the samples was measured in the accepted state.
TABLE 3 peel strength of high thermal conductivity copper clad laminate
| Peel strength (N/mm) | |
| Example 1 | 1.62 |
| Example 2 | 1.57 |
| Example 3 | 1.54 |
| Comparative example 1 | 1.06 |
| Comparative example 2 | 1.18 |
| Comparative example 3 | 1.24 |
| Comparative example 4 | 1.31 |
| Comparative example 5 | 1.12 |
Example 1 is preferred over examples 2-3 because: in silicon nitride, beta-Si in the form of large-size long rod 3 N 4 The number of various lattice defects and grain boundaries can be obviously reduced in the nucleation and growth processes of the crystal grains; conduction of heat in solid materials depends on lattice vibration, namely phonon diffusion, and lattice defects and crystal boundaries can generate scattering effect on phonons, namely heat conduction is hindered; and, the thermal conductivity of the glass phase at the grain boundary is very low, and the reduction of the number of the grain boundary means that the thermal conductivity of the whole silicon nitride is increased; ceO (CeO) 2 Has very remarkable promotion effect on grain rearrangement in the sintering process of silicon nitride, so CeO is added in the sintering process of the silicon nitride 2 Silicon nitride with higher relative density can be obtained; yb 2 O 3 Can increase the average grain size of silicon nitride and increase the content of fine grains, thereby adding CeO 2 And Yb 2 O 3 Compounding to makeThe grain size, morphology, density and microstructure of the obtained heat-conducting silicon nitride can be regulated and controlled, so that the heat-conducting adhesive layer with higher heat conductivity coefficient is obtained. The propagation of electric field in solid material is affected by crystal defects such as crystal boundary, dislocation, lattice distortion, etc., and various crystal defects can produce scattered waves with different phases and different intensities for electrons, and the application adopts CeO 2 And Yb 2 O 3 The concentration of crystal defects of the obtained heat-conducting silicon nitride crystal system can be effectively regulated and controlled by compounding, so that superposition of electron scattering waves is enhanced, the volume resistance in the whole material system is increased, the heat conductivity of the material is increased, and meanwhile, the insulation performance is enhanced, and therefore, the breakdown voltage is also increased. When the material is deformed, inherent crystal defects contained in the material can absorb deformation energy, so that damage to the material caused by deformation is delayed to a certain extent; the application adopts CeO 2 And Yb 2 O 3 The compound can effectively regulate and control the concentration of crystal defects of the obtained heat-conducting silicon nitride crystal system, thereby enhancing the deformation energy received by the heat-conducting adhesive layer when the heat-conducting adhesive layer is peeled, and further improving the peeling resistance of the material.
Example 1 is superior to comparative examples 1-4 because: the second order sintering helps to prolong the dissolution/re-precipitation process in liquid phase sintering, because the process provides diffusion power and time for the rearrangement of atoms and avoids cracking caused by lattice diffusion mismatch due to direct temperature reaching 1850 ℃, thus being beneficial to the alpha-Si 3 N 4 Conversion to beta-Si 3 N 4 Phase transformation of (C) occurs while also promoting beta-Si of large-sized long rod shape and having higher thermal conductivity 3 N 4 Nucleation and growth of (3). CeO is added with 2 And Yb 2 O 3 The grain size, morphology, density and microstructure of the obtained heat-conducting silicon nitride can be regulated and controlled by compounding, so that the heat-conducting adhesive layer with higher heat conductivity coefficient is obtained. The application adopts CeO 2 And Yb 2 O 3 The concentration of crystal defects of the obtained heat-conducting silicon nitride crystal system can be effectively regulated and controlled by compounding, so that superposition of all electron scattering waves is enhanced, and volume electricity in the whole material system is increasedThe resistance increases the thermal conductivity of the material while enhancing the insulating properties, and thus the breakdown voltage. The application adopts CeO 2 And Yb 2 O 3 The compound can effectively regulate and control the concentration of crystal defects of the obtained heat-conducting silicon nitride crystal system, thereby enhancing the deformation energy received by the heat-conducting adhesive layer when the heat-conducting adhesive layer is peeled, and further improving the peeling resistance of the material.
Example 1 is superior to comparative examples 1, 5 because: the microcapsule silicon nitride is prepared by taking n-hexadecane as a wrapping shell to establish a net structure, so that the specific surface area of the silicon nitride in a heat conducting adhesive layer is increased, and the heat exchange area is increased; the microcapsule has certain elasticity due to the alkane long chain of hexadecane, so that the microcapsule has stability against volume expansion and contraction when the temperature changes, and improves the heat conduction efficiency and the thermal cycle stability and heat resistance; the microcapsule silicon nitride prepared by the method has strong heat energy storage density and short heat response time due to the spherical wrapping structure, and is further beneficial to heat transfer. KH570 silane coupling agents increase the number of branches attached to n-hexadecane, the presence of these branches increasing the energy storage density. The alkane wrapping layer of the outer layer of the microcapsule silicon nitride prepared by the specific method has certain insulating property, so that the breakdown voltage of the material can be increased. The microcapsule silicon nitride prepared by the specific method has the advantages that the alkane wrapping layer with certain elasticity on the outer layer can provide elastic deformation within a certain safety range when the adhesive layer is subjected to tensile force, and can obviously absorb energy so as to keep the whole adhesive layer in an energy steady state without breaking.
It should be noted that the above embodiments are only for illustrating the technical solution of the present application, and not for limiting the same. While the application has been described in detail with reference to the preferred embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents substituted for elements thereof without departing from the scope of the application, which is to be encompassed by the appended claims.
Claims (3)
1. A preparation method of a high-heat-conductivity copper-clad plate is characterized by comprising the following steps: the method comprises the following steps: mixing 25-35 parts by weight of polyimide resin, 10-20 parts by weight of microcapsule silicon nitride, 1-5 parts by weight of modified graphene and 70-90 parts by weight of acetone at a temperature of 25-35 ℃ at 200-300rpm for 0.5-1.5 hours to obtain a heat conducting colloid; polishing and coarsening one plane of each of the copper plate and the aluminum plate, wherein the surface roughness is required to reach Ra=25-100; uniformly coating the heat-conducting colloid on the polished and roughened plane of the aluminum plate to form a heat-conducting adhesive layer, attaching the polished and roughened plane of the copper plate to the heat-conducting adhesive layer to obtain a three-layer sandwich-structured composite plate, and drying the composite plate at 230-250 ℃ for 1-3h to obtain the high-heat-conducting copper-clad plate;
the preparation method of the modified graphene comprises the following steps: adding graphene and 2-aminopyridine into an ethanol water solution with the weight percent of 50-65%, and performing ultrasonic treatment for 20-50min under the conditions of 20-30kHz and 200-300W, wherein the mass ratio of the graphene to the 2-aminopyridine to ethanol water solution is (6-12) (0.1-0.5): 50; adding vinyl tributyl ketoxime silane, sodium alginate and aluminum chloride, and continuing ultrasonic treatment for 50-100min, wherein the mass ratio of the vinyl tributyl ketoxime silane, the sodium alginate, the aluminum chloride and the graphene is (0.1-0.3): 1-2): 1-3): 10, so as to obtain a mixed solution I; dripping 30-50wt% sodium hydroxide aqueous solution into the mixed solution I at the temperature of 70-80 ℃ and at the speed of 100-200rpm at the speed of 1-3mL/min, and continuously stirring for 100-150min after the dripping is finished, wherein the mass ratio of the sodium hydroxide aqueous solution to the graphene is 1 (1-5); centrifuging, drying and grinding the precipitate to obtain modified graphene;
the preparation method of the microcapsule silicon nitride comprises the following steps: mixing heat-conducting silicon nitride and KH570 silane coupling agent according to the mass ratio of (0.8-1.2), and dispersing for 1.5-2.5h by using ultrasonic waves with the power of 500-700w and the frequency of 30-40 kHz; then adding 60-67% ethanol water solution by mass percent, wherein the mass ratio of the heat-conducting silicon nitride to the KH570 silane coupling agent to the ethanol water solution is (0.8-1.2) (4.5-5.5), and stirring at 160-200rpm for 3h at 75-85 ℃; drying at 125-135 deg.c for 0.5-2 hr to obtain precursor; mixing the precursor, n-hexadecane, pentaerythritol tetraacrylate, methyl tiglate and deionized water according to the mass ratio of (0.8-1.2), (18-22), (5-10), (12-17), (25-35), dispersing for 0.5-2h by using ultrasonic waves with the power of 500-700w and the frequency of 30-40kHz, and stirring at 300-400rpm for 0.5-2h at 35-45 ℃ to obtain emulsion; mixing the emulsion and isobutyronitrile according to the mass ratio of (8-12) (0.8-12), stirring at 70-80 ℃ for 12 hours at 540-660rpm, centrifuging at 1200rpm for 12 minutes to obtain a precipitate, and drying the precipitate at 65 ℃ for 12 hours to obtain the microcapsule silicon nitride;
the preparation method of the heat-conducting silicon nitride comprises the following steps: by reacting alpha-Si 3 N 4 Mixing with sintering aid (95-105) (1.2-1.8) and stirring at 60-150rpm for 0.5-1.5h to obtain prefabricated powder; heating the prefabricated powder at a heating rate of 1-2.5 ℃/min under nitrogen atmosphere, preserving heat for 1.5-2.5h when the temperature reaches 1550-1650 ℃, then continuing to heat at a heating rate of 1-2.5 ℃/min, preserving heat for 1.5-2.5h when the temperature reaches 1800-1900 ℃, cooling along with a furnace, and sieving with a 800-1200 mesh sieve after crushing to obtain the heat-conducting silicon nitride;
the sintering aid is CeO 2 、Yb 2 O 3 One or a mixture of both.
2. The method for preparing the high-heat-conductivity copper-clad plate according to claim 1, wherein the thickness of the copper-clad plate is 25-35 mu m, the thickness of the aluminum plate is 0.8-1.2mm, and the thickness of the heat-conductivity adhesive layer is 22-28 mu m.
3. The utility model provides a high heat conduction copper-clad plate which characterized in that: prepared by the method of claim 1 or 2.
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