CN113043680A - High-heat-dissipation aluminum-based copper-clad plate - Google Patents
High-heat-dissipation aluminum-based copper-clad plate Download PDFInfo
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Abstract
The invention discloses a high-heat-dissipation metal aluminum-based copper-clad plate which is formed by pressing a copper foil plate, a heat-dissipation insulating layer and an aluminum substrate which are sequentially arranged from top to bottom; the heat dissipation insulating layer comprises the following components in parts by weight: 100 parts of epoxy resin, 20-40 parts of heat-conducting filler, 2-8 parts of curing accelerator and 20-50 parts of curing agent; the heat-conducting filler is prepared by coating boron nitride on modified hollow microspheres, and the modified hollow microspheres are porous hollow microspheres prepared by compounding tantalum disilicide powder and basic cobalt carbonate. According to the invention, the epoxy resin is used as the matrix, and the added heat-conducting filler not only enhances the heat-radiating capacity of the epoxy resin, but also enhances the mechanical property of the epoxy resin, so that the heat-radiating insulating layer has the characteristics of high heat conductivity, high stability and the like, and the heat accumulated by the heating element can be quickly, timely and effectively transferred, thereby ensuring the normal operation of equipment.
Description
Technical Field
The invention relates to the field of metal-based copper-clad plates, in particular to a high-heat-dissipation metal-aluminum-based copper-clad plate.
Background
With the rapid development of electronic products in the direction of light weight, thinness, small size, high density, multiple functions and microelectronic integration technology, the volume of electronic elements and logic circuits is reduced by times, the working frequency is increased rapidly, the power consumption is increased continuously, the working environment of components is changed in the direction of high temperature, the reliability of the whole machine is reduced, and the service life is shortened. The development of a metal-based copper-clad plate with high heat dissipation performance is undoubtedly the most effective means for solving the problems of heat dissipation and structural design.
Disclosure of Invention
Aiming at the problems mentioned in the background technology, the invention provides a high-heat-dissipation metal aluminum-based copper-clad plate which is formed by pressing a copper foil plate, a heat-dissipation insulating layer and an aluminum substrate which are sequentially arranged from top to bottom;
the heat dissipation insulating layer comprises the following components in parts by weight: 100 parts of epoxy resin, 20-40 parts of heat-conducting filler, 2-8 parts of curing accelerator and 20-50 parts of curing agent;
the heat-conducting filler is prepared by coating boron nitride on modified hollow microspheres, and the modified hollow microspheres are porous hollow microspheres prepared by compounding tantalum disilicide powder and basic cobalt carbonate.
Preferably, the epoxy resin is a mixture of bisphenol A epoxy resin, naphthalene ring epoxy resin and biphenyl epoxy resin, and the weight ratio of the bisphenol A epoxy resin to the naphthalene ring epoxy resin to the biphenyl epoxy resin is 25-45: 5-10: 10-20.
Preferably, the curing agent is at least one of methyl tetrahydrophthalic anhydride, methyl hexahydrophthalic anhydride, dimer acid-based polyamide and 4, 4-diaminodiphenyl sulfone.
Preferably, the curing accelerator is 2,4, 6-tris (dimethylaminomethyl) phenol and/or N, N-dimethylbenzylamine.
Preferably, the boron nitride is a nano-grade material, and the particle size of the boron nitride is 5-20 nm.
Preferably, the particle size of the tantalum disilicide powder is 5-20 μm.
Preferably, the preparation method of the tantalum disilicide powder comprises the following steps:
respectively weighing silicon powder and tantalum powder, adding the silicon powder and the tantalum powder into a crucible, uniformly mixing, placing the crucible into a high-temperature reaction furnace, sealing the high-temperature reaction furnace, heating to 1050-1250 ℃, performing reaction treatment for 2-4 hours, cooling to 850-950 ℃, introducing hydrogen, continuing the reaction treatment for 1-2 hours, cooling to room temperature along with the furnace, collecting solids, and performing crushing treatment to obtain tantalum disilicide powder;
wherein the mass ratio of the silicon powder to the tantalum powder is 9: 28-32.
Preferably, the preparation method of the modified hollow microsphere comprises the following steps:
s1, weighing polyvinyl alcohol, adding the polyvinyl alcohol into deionized water, heating to 70-80 ℃, stirring until the polyvinyl alcohol is completely dissolved, and stirring again until the polyvinyl alcohol is completely dissolved to obtain a mixed solvent;
wherein the mass ratio of the polyvinyl alcohol to the deionized water is 1: 25-55;
s2, weighing basic cobalt carbonate, adding the basic cobalt carbonate into deionized water, heating to 45-55 ℃, and stirring until the basic cobalt carbonate is completely dissolved to obtain a basic cobalt carbonate solution;
wherein the mass ratio of the basic cobalt carbonate to the deionized water is 1: 15-28;
s3, weighing tantalum disilicide powder, adding the tantalum disilicide powder into a mixed solvent, performing ultrasonic dispersion treatment for 0.2-0.4 h at the temperature of 70-80 ℃, stirring at the speed of 600-800 rpm while dropwise adding basic cobalt carbonate solution, adding a flocculating agent after dropwise adding, continuously stirring until a small amount of aggregates are generated, reducing the stirring speed to 300-500 rpm, and then continuously stirring until the aggregates are not increased to obtain an aggregate mixed solution;
wherein the mass ratio of the tantalum disilicide powder, the mixed solvent, the basic cobalt carbonate solution and the flocculating agent is 1: 10-20: 12-18: 0.6-1.2;
s4, carrying out suction filtration on the condensate mixture while the condensate mixture is hot, rapidly pouring the collected filter residues into deionized water at the temperature of 0-10 ℃, stirring until the solid is uniformly dispersed in the water, carrying out suction filtration again, washing the collected filter residues with purified water for 3-5 times, and then treating at the temperature of 120-150 ℃ for 1-2 hours to obtain the modified hollow microspheres.
Preferably, the flocculant is one or more of aluminum sulfate, aluminum chloride, sodium chloride, ferric sulfate, aluminum sulfate, polyaluminum chloride, polyaluminum sulfate, polyferric chloride, polyferric sulfate and alum.
Preferably, the preparation method of the heat conductive filler comprises the following steps:
p1, weighing boron nitride, adding the boron nitride into deionized water, dropwise adding ammonia water until the pH value of the liquid reaches 9.5-10.5, and dispersing by ultrasonic or stirring until the liquid is uniform to obtain a boron nitride mixed liquid; weighing modified hollow microspheres, adding the modified hollow microspheres into deionized water, adding polyethylene glycol octyl phenyl ether, and dispersing by ultrasonic or stirring until the mixture is uniform to obtain a modified hollow microsphere mixed solution;
wherein in the mixed liquid of boron nitride, the mass ratio of boron nitride to deionized water is 1: 5-10; the mass ratio of the modified hollow microspheres to the polyethylene glycol octyl phenyl ether to the deionized water is 1: 0.03-0.08: 8-15;
adding the boron nitride mixed solution into the modified hollow microsphere mixed solution, performing ultrasonic treatment for 1-2 hours, pouring into a reaction kettle with a polytetrafluoroethylene lining, treating at 150-200 ℃ for 8-12 hours, naturally cooling to room temperature, filtering and collecting filter residues, washing the filter residues to be neutral by using purified water, and performing freeze drying treatment to obtain a boron nitride/modified hollow microsphere mixture;
wherein the mass ratio of the boron nitride mixed liquid to the modified hollow microsphere mixed liquid is 1: 1.36-1.84.
Preferably, the curing temperature of the epoxy resin is 100-180 ℃, and the curing time is 1-3 h.
The invention has the beneficial effects that:
1. the invention provides a high-heat-dissipation metal aluminum-based copper-clad plate which comprises a copper foil plate, a heat dissipation insulating layer and an aluminum substrate which are sequentially arranged from top to bottom, wherein the high heat dissipation performance of the copper-clad plate depends on the heat dissipation insulating layer, so that the invention improves the heat dissipation insulating layer. According to the invention, the epoxy resin is used as a matrix, and the added heat-conducting filler not only enhances the heat-dissipating capacity of the epoxy resin, but also enhances the mechanical property of the epoxy resin, so that the performance of the composite material can be improved, the interface interaction of a system can be enhanced, and the mechanical property of the composite material can be improved. The heat-radiating insulating layer has the characteristics of high heat conductivity, high stability and the like, and can quickly, timely and effectively transfer heat accumulated by the heating element to ensure the normal operation of equipment.
2. The heat-conducting filler prepared by the invention is prepared by coating boron nitride on modified hollow microspheres, and the modified hollow microspheres are porous hollow microspheres prepared by compounding tantalum disilicide powder and basic cobalt carbonate. According to the invention, by preparing the porous hollow microsphere, a large amount of boron nitride can be adsorbed and fixed, and the boron nitride can be stably fixed in the hollow microsphere, so that the boron nitride exists in a high polymer base material more stably, and the modified hollow microsphere is prepared from tantalum disilicide and cobalt which have better heat conductivity, so that the influence on the heat dissipation performance is smaller, and the modified hollow microsphere can be more uniformly and stably combined with the high polymer base material after being modified, so that the long-term heat dissipation effect can be achieved.
3. In the process of preparing the tantalum disilicide powder, the selected tantalum has a small thermal expansion coefficient and has excellent chemical properties with silicon, so that the prepared tantalum disilicide is more active compared with boron nitride and can be better crosslinked and fused with a high-molecular base material.
4. In the process of coating boron nitride on the modified hollow microspheres, the polyethylene glycol octyl phenyl ether is used as a strong surfactant, so that the surfaces and the inside of the apertures of the modified hollow microspheres can be activated, and the activated boron nitride can be more firmly loaded in the hollow microspheres.
Detailed Description
For the purpose of more clearly illustrating the present invention and more clearly understanding the technical features, objects and advantages of the present invention, the technical solutions of the present invention will now be described in detail below, but are not to be construed as limiting the implementable scope of the present invention.
Boron nitride is considered to be the most promising thermally conductive filler with its excellent thermal conductivity, excellent electrical insulation and outstanding thermal stability. However, the surface of boron nitride lacks active functional groups, and the chemical properties are too stable, so that boron nitride nanoparticles are difficult to be infiltrated and compatible with the polymer substrate, the dispersibility is poor, the boron nitride nanoparticles are easy to agglomerate, and the addition amount of boron nitride is limited to the maximum extent, so that the heat dissipation performance of the polymer substrate is enhanced, and when the addition amount of boron nitride is further increased, the mechanical properties of the polymer substrate are greatly reduced. In the prior art, most of boron nitride is subjected to silanization modification or polymer coating modification, although the activity of boron nitride can be improved to a certain extent, the heat-conducting property of silicon nitride is greatly reduced by the polymer coating modification, and silane on the surface of the boron nitride is decomposed after the silanization modification of the boron nitride is applied for a period of time. Therefore, the porous hollow microspheres can adsorb and fix a large amount of boron nitride, and can stably fix the boron nitride in the hollow microspheres, so that the boron nitride is more stably existed in a high polymer base material, and the modified hollow microspheres are prepared from tantalum disilicide and cobalt with better heat conductivity, so that the influence on heat dissipation performance is less, and the modified hollow microspheres can be more uniformly and stably combined with the high polymer base material after being modified, so that the long-term heat dissipation effect can be achieved.
In the preparation process of the modified hollow microsphere, tantalum disilicide powder is used as a base material, basic cobalt carbonate is added as an auxiliary material, in the preparation process, the tantalum disilicide powder and the basic cobalt carbonate generate the hollow microsphere under the action of a salt template, in the process, partial basic cobalt carbonate is decomposed to form gullies in the hollow microsphere, a small amount of air holes are formed in an outer shell, then the basic cobalt carbonate is completely decomposed through further high-temperature treatment, a large amount of air holes are formed in the outer shell, the air holes are increased and enlarged, and therefore a hollow microsphere structure with multiple gullies in the porous inner surface is formed, the structure has a very large specific surface area, boron nitride can conveniently enter the interior of the microsphere to fix more boron nitride with high heat dissipation performance, and when the modified hollow microsphere is combined with a high polymer substrate, the high polymer substrate can form a more stable clamping structure with the microsphere through the porous structure on the surface, therefore, the heat dissipation performance is enhanced, the compatibility with the polymer base material is also enhanced, and in addition, the mechanical property of the polymer base material is also enhanced.
The invention is further described with reference to the following examples.
Example 1
A high heat dissipation metal aluminum base copper-clad plate is formed by pressing a copper foil plate, a heat dissipation insulating layer and an aluminum base plate which are sequentially arranged from top to bottom;
the heat dissipation insulating layer comprises the following components in parts by weight:
100 parts of epoxy resin, 30 parts of heat-conducting filler, 6 parts of curing accelerator and 35 parts of curing agent;
the heat-conducting filler is prepared by coating boron nitride on modified hollow microspheres, and the modified hollow microspheres are porous hollow microspheres prepared by compounding tantalum disilicide powder and basic cobalt carbonate.
The epoxy resin is a mixture of bisphenol A epoxy resin, naphthalene ring epoxy resin and biphenyl epoxy resin, and the weight ratio of the bisphenol A epoxy resin to the naphthalene ring epoxy resin to the biphenyl epoxy resin is 32:8: 15.
The curing agent is methyl tetrahydrophthalic anhydride.
The curing accelerator is 2,4, 6-tri (dimethylaminomethyl) phenol.
The boron nitride is a nano-grade material, and the particle size of the boron nitride is 5-20 nm.
The particle size of the tantalum disilicide powder is 5-20 microns.
The preparation method of the tantalum disilicide powder comprises the following steps:
respectively weighing silicon powder and tantalum powder, adding the silicon powder and the tantalum powder into a crucible, uniformly mixing, placing the crucible into a high-temperature reaction furnace, sealing the high-temperature reaction furnace, heating to 1050-1250 ℃, performing reaction treatment for 2-4 hours, cooling to 850-950 ℃, introducing hydrogen, continuing the reaction treatment for 1-2 hours, cooling to room temperature along with the furnace, collecting solids, and performing crushing treatment to obtain tantalum disilicide powder;
wherein the mass ratio of the silicon powder to the tantalum powder is 9: 30.
The preparation method of the modified hollow microsphere comprises the following steps:
s1, weighing polyvinyl alcohol, adding the polyvinyl alcohol into deionized water, heating to 70-80 ℃, stirring until the polyvinyl alcohol is completely dissolved, and stirring again until the polyvinyl alcohol is completely dissolved to obtain a mixed solvent;
wherein the mass ratio of the polyvinyl alcohol to the deionized water is 1: 38;
s2, weighing basic cobalt carbonate, adding the basic cobalt carbonate into deionized water, heating to 45-55 ℃, and stirring until the basic cobalt carbonate is completely dissolved to obtain a basic cobalt carbonate solution;
wherein the mass ratio of the basic cobalt carbonate to the deionized water is 1: 22;
s3, weighing tantalum disilicide powder, adding the tantalum disilicide powder into a mixed solvent, performing ultrasonic dispersion treatment for 0.2-0.4 h at the temperature of 70-80 ℃, stirring at the speed of 600-800 rpm while dropwise adding basic cobalt carbonate solution, adding a flocculating agent after dropwise adding, continuously stirring until a small amount of aggregates are generated, reducing the stirring speed to 300-500 rpm, and then continuously stirring until the aggregates are not increased to obtain an aggregate mixed solution;
wherein the mass ratio of the tantalum disilicide powder, the mixed solvent, the basic cobalt carbonate solution and the flocculating agent is 1:15:16: 0.9;
s4, carrying out suction filtration on the condensate mixture while the condensate mixture is hot, rapidly pouring the collected filter residues into deionized water at the temperature of 0-10 ℃, stirring until the solid is uniformly dispersed in the water, carrying out suction filtration again, washing the collected filter residues with purified water for 3-5 times, and then treating at the temperature of 120-150 ℃ for 1-2 hours to obtain the modified hollow microspheres.
The flocculating agent is aluminum sulfate.
The preparation method of the heat-conducting filler comprises the following steps:
p1, weighing boron nitride, adding the boron nitride into deionized water, dropwise adding ammonia water until the pH value of the liquid reaches 9.5-10.5, and dispersing by ultrasonic or stirring until the liquid is uniform to obtain a boron nitride mixed liquid; weighing modified hollow microspheres, adding the modified hollow microspheres into deionized water, adding polyethylene glycol octyl phenyl ether, and dispersing by ultrasonic or stirring until the mixture is uniform to obtain a modified hollow microsphere mixed solution;
wherein in the mixed liquid of boron nitride, the mass ratio of boron nitride to deionized water is 1: 8; the mass ratio of the modified hollow microspheres to the polyethylene glycol octyl phenyl ether to the deionized water is 1:0.05: 12;
adding the boron nitride mixed solution into the modified hollow microsphere mixed solution, performing ultrasonic treatment for 1-2 hours, pouring into a reaction kettle with a polytetrafluoroethylene lining, treating at 150-200 ℃ for 8-12 hours, naturally cooling to room temperature, filtering and collecting filter residues, washing the filter residues to be neutral by using purified water, and performing freeze drying treatment to obtain a boron nitride/modified hollow microsphere mixture;
wherein the mass ratio of the boron nitride mixed liquid to the modified hollow microsphere mixed liquid is 1: 1.58.
The curing temperature of the epoxy resin is 150 ℃, and the curing time is 2 h.
Example 2
A high heat dissipation metal aluminum base copper-clad plate is formed by pressing a copper foil plate, a heat dissipation insulating layer and an aluminum base plate which are sequentially arranged from top to bottom;
the heat dissipation insulating layer comprises the following components in parts by weight:
100 parts of epoxy resin, 20 parts of heat-conducting filler, 2 parts of curing accelerator and 20 parts of curing agent;
the heat-conducting filler is prepared by coating boron nitride on modified hollow microspheres, and the modified hollow microspheres are porous hollow microspheres prepared by compounding tantalum disilicide powder and basic cobalt carbonate.
The epoxy resin is a mixture of bisphenol A epoxy resin, naphthalene ring epoxy resin and biphenyl epoxy resin, and the weight ratio of the bisphenol A epoxy resin to the naphthalene ring epoxy resin to the biphenyl epoxy resin is 25:5: 10.
The curing agent is dimer acid-based polyamide.
The curing accelerator is N, N-dimethylbenzylamine.
The boron nitride is a nano-grade material, and the particle size of the boron nitride is 5-20 nm.
The particle size of the tantalum disilicide powder is 5-20 microns.
The preparation method of the tantalum disilicide powder comprises the following steps:
respectively weighing silicon powder and tantalum powder, adding the silicon powder and the tantalum powder into a crucible, uniformly mixing, placing the crucible into a high-temperature reaction furnace, sealing the high-temperature reaction furnace, heating to 1050-1250 ℃, performing reaction treatment for 2-4 hours, cooling to 850-950 ℃, introducing hydrogen, continuing the reaction treatment for 1-2 hours, cooling to room temperature along with the furnace, collecting solids, and performing crushing treatment to obtain tantalum disilicide powder;
wherein the mass ratio of the silicon powder to the tantalum powder is 9: 28.
The preparation method of the modified hollow microsphere comprises the following steps:
s1, weighing polyvinyl alcohol, adding the polyvinyl alcohol into deionized water, heating to 70-80 ℃, stirring until the polyvinyl alcohol is completely dissolved, and stirring again until the polyvinyl alcohol is completely dissolved to obtain a mixed solvent;
wherein the mass ratio of the polyvinyl alcohol to the deionized water is 1: 25;
s2, weighing basic cobalt carbonate, adding the basic cobalt carbonate into deionized water, heating to 45-55 ℃, and stirring until the basic cobalt carbonate is completely dissolved to obtain a basic cobalt carbonate solution;
wherein the mass ratio of the basic cobalt carbonate to the deionized water is 1: 15;
s3, weighing tantalum disilicide powder, adding the tantalum disilicide powder into a mixed solvent, performing ultrasonic dispersion treatment for 0.2-0.4 h at the temperature of 70-80 ℃, stirring at the speed of 600-800 rpm while dropwise adding basic cobalt carbonate solution, adding a flocculating agent after dropwise adding, continuously stirring until a small amount of aggregates are generated, reducing the stirring speed to 300-500 rpm, and then continuously stirring until the aggregates are not increased to obtain an aggregate mixed solution;
wherein the mass ratio of the tantalum disilicide powder, the mixed solvent, the basic cobalt carbonate solution and the flocculating agent is 1:10:12: 0.6;
s4, carrying out suction filtration on the condensate mixture while the condensate mixture is hot, rapidly pouring the collected filter residues into deionized water at the temperature of 0-10 ℃, stirring until the solid is uniformly dispersed in the water, carrying out suction filtration again, washing the collected filter residues with purified water for 3-5 times, and then treating at the temperature of 120-150 ℃ for 1-2 hours to obtain the modified hollow microspheres.
The flocculant is ferric chloride.
The preparation method of the heat-conducting filler comprises the following steps:
p1, weighing boron nitride, adding the boron nitride into deionized water, dropwise adding ammonia water until the pH value of the liquid reaches 9.5-10.5, and dispersing by ultrasonic or stirring until the liquid is uniform to obtain a boron nitride mixed liquid; weighing modified hollow microspheres, adding the modified hollow microspheres into deionized water, adding polyethylene glycol octyl phenyl ether, and dispersing by ultrasonic or stirring until the mixture is uniform to obtain a modified hollow microsphere mixed solution;
wherein in the mixed liquid of boron nitride, the mass ratio of boron nitride to deionized water is 1: 5; the mass ratio of the modified hollow microspheres to the polyethylene glycol octyl phenyl ether to the deionized water is 1:0.03: 8;
adding the boron nitride mixed solution into the modified hollow microsphere mixed solution, performing ultrasonic treatment for 1-2 hours, pouring into a reaction kettle with a polytetrafluoroethylene lining, treating at 150-200 ℃ for 8-12 hours, naturally cooling to room temperature, filtering and collecting filter residues, washing the filter residues to be neutral by using purified water, and performing freeze drying treatment to obtain a boron nitride/modified hollow microsphere mixture;
wherein the mass ratio of the boron nitride mixed liquid to the modified hollow microsphere mixed liquid is 1: 1.36.
The curing temperature of the epoxy resin is 100 ℃, and the curing time is 1 h.
Example 3
A high heat dissipation metal aluminum base copper-clad plate is formed by pressing a copper foil plate, a heat dissipation insulating layer and an aluminum base plate which are sequentially arranged from top to bottom;
the heat dissipation insulating layer comprises the following components in parts by weight:
100 parts of epoxy resin, 40 parts of heat-conducting filler, 8 parts of curing accelerator and 50 parts of curing agent;
the heat-conducting filler is prepared by coating boron nitride on modified hollow microspheres, and the modified hollow microspheres are porous hollow microspheres prepared by compounding tantalum disilicide powder and basic cobalt carbonate.
The epoxy resin is a mixture of bisphenol A epoxy resin, naphthalene ring epoxy resin and biphenyl epoxy resin, and the weight ratio of the bisphenol A epoxy resin to the naphthalene ring epoxy resin to the biphenyl epoxy resin is 45:10: 20.
The curing agent is 4, 4-diaminodiphenyl sulfone.
The curing accelerator is 2,4, 6-tri (dimethylaminomethyl) phenol.
The boron nitride is a nano-grade material, and the particle size of the boron nitride is 5-20 nm.
The particle size of the tantalum disilicide powder is 5-20 microns.
The preparation method of the tantalum disilicide powder comprises the following steps:
respectively weighing silicon powder and tantalum powder, adding the silicon powder and the tantalum powder into a crucible, uniformly mixing, placing the crucible into a high-temperature reaction furnace, sealing the high-temperature reaction furnace, heating to 1050-1250 ℃, performing reaction treatment for 2-4 hours, cooling to 850-950 ℃, introducing hydrogen, continuing the reaction treatment for 1-2 hours, cooling to room temperature along with the furnace, collecting solids, and performing crushing treatment to obtain tantalum disilicide powder;
wherein the mass ratio of the silicon powder to the tantalum powder is 9: 32.
The preparation method of the modified hollow microsphere comprises the following steps:
s1, weighing polyvinyl alcohol, adding the polyvinyl alcohol into deionized water, heating to 70-80 ℃, stirring until the polyvinyl alcohol is completely dissolved, and stirring again until the polyvinyl alcohol is completely dissolved to obtain a mixed solvent;
wherein the mass ratio of the polyvinyl alcohol to the deionized water is 1: 55;
s2, weighing basic cobalt carbonate, adding the basic cobalt carbonate into deionized water, heating to 45-55 ℃, and stirring until the basic cobalt carbonate is completely dissolved to obtain a basic cobalt carbonate solution;
wherein the mass ratio of the basic cobalt carbonate to the deionized water is 1: 28;
s3, weighing tantalum disilicide powder, adding the tantalum disilicide powder into a mixed solvent, performing ultrasonic dispersion treatment for 0.2-0.4 h at the temperature of 70-80 ℃, stirring at the speed of 600-800 rpm while dropwise adding basic cobalt carbonate solution, adding a flocculating agent after dropwise adding, continuously stirring until a small amount of aggregates are generated, reducing the stirring speed to 300-500 rpm, and then continuously stirring until the aggregates are not increased to obtain an aggregate mixed solution;
wherein the mass ratio of the tantalum disilicide powder, the mixed solvent, the basic cobalt carbonate solution and the flocculating agent is 1:20:18: 1.2;
s4, carrying out suction filtration on the condensate mixture while the condensate mixture is hot, rapidly pouring the collected filter residues into deionized water at the temperature of 0-10 ℃, stirring until the solid is uniformly dispersed in the water, carrying out suction filtration again, washing the collected filter residues with purified water for 3-5 times, and then treating at the temperature of 120-150 ℃ for 1-2 hours to obtain the modified hollow microspheres.
The flocculating agent is alum.
The preparation method of the heat-conducting filler comprises the following steps:
p1, weighing boron nitride, adding the boron nitride into deionized water, dropwise adding ammonia water until the pH value of the liquid reaches 9.5-10.5, and dispersing by ultrasonic or stirring until the liquid is uniform to obtain a boron nitride mixed liquid; weighing modified hollow microspheres, adding the modified hollow microspheres into deionized water, adding polyethylene glycol octyl phenyl ether, and dispersing by ultrasonic or stirring until the mixture is uniform to obtain a modified hollow microsphere mixed solution;
wherein in the mixed liquid of boron nitride, the mass ratio of boron nitride to deionized water is 1: 10; the mass ratio of the modified hollow microspheres to the polyethylene glycol octyl phenyl ether to the deionized water is 1:0.08: 15;
adding the boron nitride mixed solution into the modified hollow microsphere mixed solution, performing ultrasonic treatment for 1-2 hours, pouring into a reaction kettle with a polytetrafluoroethylene lining, treating at 150-200 ℃ for 8-12 hours, naturally cooling to room temperature, filtering and collecting filter residues, washing the filter residues to be neutral by using purified water, and performing freeze drying treatment to obtain a boron nitride/modified hollow microsphere mixture;
wherein the mass ratio of the boron nitride mixed liquid to the modified hollow microsphere mixed liquid is 1: 1.84.
The curing temperature of the epoxy resin is 180 ℃, and the curing time is 3 h.
Comparative example 1
A high heat dissipation metal aluminum base copper-clad plate is formed by pressing a copper foil plate, a heat dissipation insulating layer and an aluminum base plate which are sequentially arranged from top to bottom;
the heat dissipation insulating layer comprises the following components in parts by weight:
100 parts of epoxy resin, 30 parts of heat-conducting filler, 6 parts of curing accelerator and 35 parts of curing agent;
wherein the heat conducting filler is boron nitride.
The epoxy resin is a mixture of bisphenol A epoxy resin, naphthalene ring epoxy resin and biphenyl epoxy resin, and the weight ratio of the bisphenol A epoxy resin to the naphthalene ring epoxy resin to the biphenyl epoxy resin is 32:8: 15.
The curing agent is methyl tetrahydrophthalic anhydride.
The curing accelerator is 2,4, 6-tri (dimethylaminomethyl) phenol.
The boron nitride is a nano-grade material, and the particle size of the boron nitride is 5-20 nm.
The curing temperature of the epoxy resin is 150 ℃, and the curing time is 2 h.
Comparative example 2
A high heat dissipation metal aluminum base copper-clad plate is formed by pressing a copper foil plate, a heat dissipation insulating layer and an aluminum base plate which are sequentially arranged from top to bottom;
the heat dissipation insulating layer comprises the following components in parts by weight:
100 parts of epoxy resin, 30 parts of heat-conducting filler, 6 parts of curing accelerator and 35 parts of curing agent;
the heat-conducting filler is prepared by mixing tantalum disilicide powder and boron nitride according to the mass ratio of 1:1.
The epoxy resin is a mixture of bisphenol A epoxy resin, naphthalene ring epoxy resin and biphenyl epoxy resin, and the weight ratio of the bisphenol A epoxy resin to the naphthalene ring epoxy resin to the biphenyl epoxy resin is 32:8: 15.
The curing agent is methyl tetrahydrophthalic anhydride.
The curing accelerator is 2,4, 6-tri (dimethylaminomethyl) phenol.
The boron nitride is a nano-grade material, and the particle size of the boron nitride is 5-20 nm.
The particle size of the tantalum disilicide powder is 5-20 microns.
The preparation method of the tantalum disilicide powder comprises the following steps:
respectively weighing silicon powder and tantalum powder, adding the silicon powder and the tantalum powder into a crucible, uniformly mixing, placing the crucible into a high-temperature reaction furnace, sealing the high-temperature reaction furnace, heating to 1050-1250 ℃, performing reaction treatment for 2-4 hours, cooling to 850-950 ℃, introducing hydrogen, continuing the reaction treatment for 1-2 hours, cooling to room temperature along with the furnace, collecting solids, and performing crushing treatment to obtain tantalum disilicide powder;
wherein the mass ratio of the silicon powder to the tantalum powder is 9: 30.
The curing temperature of the epoxy resin is 150 ℃, and the curing time is 2 h.
The heat-conducting property and the mechanical property of the heat-radiating insulating layers prepared in the embodiments 1 to 3 and the comparative examples 1 to 2 are detected, the tensile strength is detected according to the standard GB1042-1979, the bending strength is detected according to the standard GB1042-1979, the thermal conductivity is detected by using a DRH-300 thermal conductivity tester of Shanghai Hongyo instruments and Equipment Limited, and the results of the heat-radiating insulating layers are shown in Table 1.
Table 1 property test results of different heat-dissipating insulation layers
As can be seen from Table 1, the high-heat-dissipation aluminum-based copper clad laminate prepared in the embodiments 1 to 3 of the present invention has a higher thermal conductivity than the conventional epoxy heat dissipation layer, and has higher tensile strength and bending strength.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention, and not for limiting the protection scope of the present invention, although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (10)
1. A high heat dissipation metal aluminum base copper-clad plate is characterized in that the copper aluminum base copper-clad plate is formed by pressing a copper foil plate, a heat dissipation insulating layer and an aluminum base plate which are sequentially arranged from top to bottom;
the heat dissipation insulating layer comprises the following components in parts by weight: 100 parts of epoxy resin, 20-40 parts of heat-conducting filler, 2-8 parts of curing accelerator and 20-50 parts of curing agent;
the heat-conducting filler is prepared by coating boron nitride on modified hollow microspheres, and the modified hollow microspheres are porous hollow microspheres prepared by compounding tantalum disilicide powder and basic cobalt carbonate.
2. The high-heat-dissipation metal aluminum-based copper-clad plate according to claim 1, wherein the epoxy resin is a mixture of bisphenol A epoxy resin, naphthalene ring epoxy resin and biphenyl epoxy resin, and the weight ratio of the bisphenol A epoxy resin to the naphthalene ring epoxy resin to the biphenyl epoxy resin is 25-45: 5-10: 10-20.
3. The high-heat-dissipation metal aluminum-based copper-clad plate according to claim 1, wherein the curing agent is at least one of methyl tetrahydrophthalic anhydride, methyl hexahydrophthalic anhydride, dimer acid-based polyamide, and 4, 4-diaminodiphenyl sulfone.
4. The high-heat-dissipation metallic aluminum-based copper-clad plate according to claim 1, wherein the curing accelerator is 2,4, 6-tris (dimethylaminomethyl) phenol and/or N, N-dimethylbenzylamine.
5. The high-heat-dissipation metal aluminum-based copper-clad plate according to claim 1, wherein the boron nitride is a nano-scale material, and the particle size of the boron nitride is 5-20 nm.
6. The high-heat-dissipation metal aluminum-based copper-clad plate according to claim 1, wherein the particle size of the tantalum disilicide powder is 5-20 μm.
7. The high-heat-dissipation metal aluminum-based copper-clad plate according to claim 1, wherein the preparation method of the modified hollow microspheres comprises the following steps:
s1, weighing polyvinyl alcohol, adding the polyvinyl alcohol into deionized water, heating to 70-80 ℃, stirring until the polyvinyl alcohol is completely dissolved, and stirring again until the polyvinyl alcohol is completely dissolved to obtain a mixed solvent;
wherein the mass ratio of the polyvinyl alcohol to the deionized water is 1: 25-55;
s2, weighing basic cobalt carbonate, adding the basic cobalt carbonate into deionized water, heating to 45-55 ℃, and stirring until the basic cobalt carbonate is completely dissolved to obtain a basic cobalt carbonate solution;
wherein the mass ratio of the basic cobalt carbonate to the deionized water is 1: 15-28;
s3, weighing tantalum disilicide powder, adding the tantalum disilicide powder into a mixed solvent, performing ultrasonic dispersion treatment for 0.2-0.4 h at the temperature of 70-80 ℃, stirring at the speed of 600-800 rpm while dropwise adding basic cobalt carbonate solution, adding a flocculating agent after dropwise adding, continuously stirring until a small amount of aggregates are generated, reducing the stirring speed to 300-500 rpm, and then continuously stirring until the aggregates are not increased to obtain an aggregate mixed solution;
wherein the mass ratio of the tantalum disilicide powder, the mixed solvent, the basic cobalt carbonate solution and the flocculating agent is 1: 10-20: 12-18: 0.6-1.2;
s4, carrying out suction filtration on the condensate mixture while the condensate mixture is hot, rapidly pouring the collected filter residues into deionized water at the temperature of 0-10 ℃, stirring until the solid is uniformly dispersed in the water, carrying out suction filtration again, washing the collected filter residues with purified water for 3-5 times, and then treating at the temperature of 120-150 ℃ for 1-2 hours to obtain the modified hollow microspheres.
8. The high-heat-dissipation metallic aluminum-based copper-clad plate according to claim 7, wherein the flocculant is one or more of aluminum sulfate, aluminum chloride, sodium chloride, ferric sulfate, aluminum sulfate, polyaluminum chloride, polyaluminum sulfate, polyferric chloride, polyferric sulfate and alum.
9. The high-heat-dissipation metal aluminum-based copper-clad plate according to claim 1, wherein the preparation method of the heat-conducting filler comprises the following steps:
p1, weighing boron nitride, adding the boron nitride into deionized water, dropwise adding ammonia water until the pH value of the liquid reaches 9.5-10.5, and dispersing by ultrasonic or stirring until the liquid is uniform to obtain a boron nitride mixed liquid; weighing modified hollow microspheres, adding the modified hollow microspheres into deionized water, adding polyethylene glycol octyl phenyl ether, and dispersing by ultrasonic or stirring until the mixture is uniform to obtain a modified hollow microsphere mixed solution;
wherein in the mixed liquid of boron nitride, the mass ratio of boron nitride to deionized water is 1: 5-10; the mass ratio of the modified hollow microspheres to the polyethylene glycol octyl phenyl ether to the deionized water is 1: 0.03-0.08: 8-15;
adding the boron nitride mixed solution into the modified hollow microsphere mixed solution, performing ultrasonic treatment for 1-2 hours, pouring into a reaction kettle with a polytetrafluoroethylene lining, treating at 150-200 ℃ for 8-12 hours, naturally cooling to room temperature, filtering and collecting filter residues, washing the filter residues to be neutral by using purified water, and performing freeze drying treatment to obtain a boron nitride/modified hollow microsphere mixture;
wherein the mass ratio of the boron nitride mixed liquid to the modified hollow microsphere mixed liquid is 1: 1.36-1.84.
10. The high-heat-dissipation metal aluminum-based copper-clad plate according to claim 1, wherein the curing temperature of the epoxy resin is 100-180 ℃ and the curing time is 1-3 h.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114025472A (en) * | 2021-11-12 | 2022-02-08 | 百强电子（深圳）有限公司 | High-heat-dissipation metal-based printed circuit board and manufacturing method thereof |
| CN116471780A (en) * | 2023-04-24 | 2023-07-21 | 安徽省安瑞机电科技有限公司 | Oxygen sensor heat dissipation shell for pilot mask and preparation method thereof |
| CN117603555A (en) * | 2024-01-24 | 2024-02-27 | 四川大学 | High-heat-conductivity high-toughness epoxy resin composite material and preparation method and application thereof |
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2021
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114025472A (en) * | 2021-11-12 | 2022-02-08 | 百强电子（深圳）有限公司 | High-heat-dissipation metal-based printed circuit board and manufacturing method thereof |
| CN116471780A (en) * | 2023-04-24 | 2023-07-21 | 安徽省安瑞机电科技有限公司 | Oxygen sensor heat dissipation shell for pilot mask and preparation method thereof |
| CN116471780B (en) * | 2023-04-24 | 2024-02-23 | 安徽省安瑞机电科技有限公司 | Oxygen sensor heat dissipation shell for pilot mask |
| CN117603555A (en) * | 2024-01-24 | 2024-02-27 | 四川大学 | High-heat-conductivity high-toughness epoxy resin composite material and preparation method and application thereof |
| CN117603555B (en) * | 2024-01-24 | 2024-03-22 | 四川大学 | High-heat-conductivity high-toughness epoxy resin composite material and preparation method and application thereof |
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