WO2016078432A1 - 改性氧化铝复合材料、覆铜基板及其制备方法 - Google Patents

改性氧化铝复合材料、覆铜基板及其制备方法 Download PDF

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WO2016078432A1
WO2016078432A1 PCT/CN2015/084011 CN2015084011W WO2016078432A1 WO 2016078432 A1 WO2016078432 A1 WO 2016078432A1 CN 2015084011 W CN2015084011 W CN 2015084011W WO 2016078432 A1 WO2016078432 A1 WO 2016078432A1
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parts
copper
alumina particles
modified alumina
modified
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French (fr)
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曾小亮
孙蓉
郭坤
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Shenzhen Institute of Advanced Technology of CAS
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Shenzhen Institute of Advanced Technology of CAS
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    • 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
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/092—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising epoxy resins
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/04—Layered products comprising a layer of synthetic resin as impregnant, bonding, or embedding substance
    • 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
    • B32B37/06—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
    • 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
    • B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
    • C08K13/06—Pretreated ingredients and ingredients covered by the main groups C08K3/00 - C08K7/00
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/10—Silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • 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

Definitions

  • the invention relates to the field of preparation of a copper-clad substrate, in particular to a modified alumina composite material, a copper-clad substrate using the modified alumina composite material and a preparation method thereof.
  • the copper-clad substrate is a plate-like material obtained by immersing an electronic fiberglass cloth or other reinforcing material with a resin, and coating the copper foil on one or both sides and hot pressing.
  • the copper-clad substrate mainly provides three functions of heat conduction, insulation and support for the chip, and is a key raw material for manufacturing printed circuit boards (PCBs).
  • PCBs printed circuit boards
  • Alumina is by far the most commonly used substrate material in the microelectronics industry because it is superior to ceramic particle silica commonly used in substrate materials in mechanical, thermal, and electrical properties.
  • the alumina raw material is abundant, the price is low, the thermal stability is high, and the alumina is stable in an oxidation and reduction atmosphere up to 1925 ° C.
  • the ideal thermal conductivity of alumina reaches 30 W/m ⁇ K, and the uniform addition of alumina particles to the copper-clad substrate can greatly improve the mechanical properties and thermal properties of the substrate material.
  • the alumina particles have a large specific surface area and a high surface energy, so that the alumina particles are easily aggregated, and the alumina is more difficult to be uniform in the polymer matrix due to the lower force between the alumina and the polymer. Distribution, the conventional copper-clad substrate containing alumina particles is prone to clustering.
  • a modified alumina composite material comprising 35 parts to 55 parts of modified alumina particles, 25 parts to 35 parts of reinforcing fibers, 15 parts to 35 parts of liquid crystal epoxy resin, 10 parts to 21 parts by mass fraction. Curing And 0.1 part to 1 part of a promoter;
  • the modified alumina particles are obtained by modifying silane coupling agent alumina particles, and the modified alumina particles have a particle diameter of 100 nm to 1000 nm.
  • the silane coupling agent modifies the alumina particles as follows: the alumina particles are added to a solvent and ultrasonically dispersed, and the temperature is raised to 50° C. to 60° C., and the silane coupling is added. Then, the mixture is heated to 70 ° C for 4 h to 5 h, and after cooling, the filter residue is retained, and the filter residue is dried to be the modified alumina particles, wherein the silane coupling agent and the alumina particles are The mass ratio is 3:100.
  • the silane coupling agent is ⁇ -aminopropyltriethoxysilane, ⁇ -(2,3-epoxypropoxy)propyltrimethoxysilane or ⁇ -methacryloyloxyl Propyltrimethoxysilane.
  • the reinforcing fibers are regularly cross-aligned in the X-Y axis direction.
  • the reinforcing fibers are silicon carbide fibers.
  • the silicon carbide fibers are composed of 80 to 120 monofilaments, each of which has a diameter of 12 ⁇ m to 13 ⁇ m.
  • the liquid crystal epoxy resin is 3,3',5,5'-tetramethylbiphenyl diglycidyl ether, bisphenol A diglycidyl ether, 4,4'-dihydroxybiphenyl At least one of diglycidyl ether and 4,4'-dihydroxybinaphthyl diglycidyl ether.
  • the curing agent is at least one of 4,4'-dihydroxybiphenyl, 4,4'-diaminobiphenyl, and 4,4'-diaminodiphenyl sulfone.
  • liquid crystal epoxy resin is in an equal stoichiometric ratio to the curing agent.
  • the promoter is at least one of triphenylphosphine, imidazole, and chromium acetylacetonate.
  • a copper-clad substrate comprising a first electrode layer, a dielectric layer and a second electrode layer which are sequentially stacked; wherein the material of the dielectric layer is the modified alumina composite material described above.
  • the material of the first electrode layer is at least one of copper, brass, aluminum, and nickel
  • the second electrode layer is at least one of copper, brass, aluminum, and nickel
  • a method for preparing a copper-clad substrate comprises the following steps:
  • the prepreg is placed between the first electrode layer and the second electrode layer, and then hot pressed at a temperature of from 120 ° C to 200 ° C under a pressure of 5 kgf / cm 2 to 30 kgf / cm 2 for 4 h to 10 h, and finally solidified.
  • the copper clad substrate is placed between the first electrode layer and the second electrode layer, and then hot pressed at a temperature of from 120 ° C to 200 ° C under a pressure of 5 kgf / cm 2 to 30 kgf / cm 2 for 4 h to 10 h, and finally solidified.
  • the copper clad substrate is placed between the first electrode layer and the second electrode layer, and then hot pressed at a temperature of from 120 ° C to 200 ° C under a pressure of 5 kgf / cm 2 to 30 kgf / cm 2 for 4 h to 10 h, and finally solidified.
  • the copper clad substrate is placed between the first electrode layer and the second electrode layer, and then hot pressed at a temperature of from 120
  • the modified alumina particles are prepared by adding the alumina particles to a solvent for ultrasonic dispersion, heating to 50 ° C to 60 ° C, adding the silane coupling agent, followed by stirring and heating. The reaction is carried out at 70 ° C for 4 h to 5 h. After cooling, the filter residue is filtered and retained. After the filter residue is dried, the modified alumina particles are obtained.
  • the mass ratio of the silane coupling agent to the alumina particles is 3: 100.
  • the silane coupling agent is ⁇ -aminopropyltriethoxysilane, ⁇ -(2,3-epoxypropoxy)propyltrimethoxysilane or ⁇ -methacryloyloxyl
  • the propyltrimethoxysilane has a mass ratio of the silane coupling agent to the alumina particles of 3:100.
  • the operation of arranging 25 to 35 parts of the reinforcing fibers on the centrifugal film is: 25 to 35 parts of the reinforcing fibers are regularly cross-aligned on the centrifugal film in the XY-axis direction,
  • the reinforcing fiber is a silicon carbide fiber.
  • the silicon carbide fibers are composed of 80 to 120 monofilaments, each of which has a diameter of 12 ⁇ m to 13 ⁇ m.
  • the liquid crystal epoxy resin is 3,3',5,5'-tetramethylbiphenyl diglycidyl ether, bisphenol A diglycidyl ether, 4,4'-dihydroxybiphenyl At least one of diglycidyl ether and 4,4'-dihydroxybinaphthyl diglycidyl ether;
  • the curing agent is at least one of 4,4'-dihydroxybiphenyl, 4,4'-diaminobiphenyl and 4,4'-diaminodiphenyl sulfone;
  • liquid crystal epoxy resin and the curing agent are in an equal stoichiometric ratio.
  • the centrifuge film is made of polyethylene terephthalate.
  • the modified alumina composite material comprises modified alumina particles, reinforcing fibers and liquid crystal epoxy resin, and the modified alumina particles are obtained by modifying the alumina particles with a silane coupling agent.
  • the alumina particles are modified by a silane coupling agent to form an active chemical group such as an amino group or a hydroxyl group, and the alumina particles are chemically bonded to the liquid crystal epoxy resin through a reactive group such as an amino group or a hydroxyl group formed on the surface, thereby improving the interface.
  • the interaction reduces the thermal resistance of the interface and reduces the cluster phenomenon. Compared with traditional composite materials, this modified alumina composite is not prone to clustering.
  • FIG. 1 is a flow chart showing a method of manufacturing a copper clad substrate according to an embodiment
  • Example 2 is a SEM photograph of dispersion of alumina particles in Example 1 in an organic solvent
  • Example 3 is a SEM photograph of dispersion of ⁇ -aminopropyltriethoxysilane-modified alumina particles prepared in Example 1 in an organic solvent;
  • Figure 4 is a cross-sectional electron micrograph of the prepreg obtained in Example 1;
  • Figure 5 is a cross-sectional electron micrograph of the prepreg obtained in Example 1.
  • the modified alumina composite material includes 35 parts to 55 parts of modified alumina particles, 25 parts to 35 parts of reinforcing fibers, 15 parts to 35 parts of liquid crystal epoxy resin, and 10 parts by mass. 21 parts of curing agent and 0.1 part to 1 part of accelerator.
  • the modified alumina particles are obtained by modifying the alumina particles with a silane coupling agent.
  • the modified alumina particles may have a particle diameter of from 100 nm to 1000 nm.
  • the modified alumina particles have a particle size of 700 nm.
  • the silane coupling agent is ⁇ -aminopropyltriethoxysilane, ⁇ -(2,3-epoxypropoxy)propyltrimethoxysilane or ⁇ -methacryloxypropyltrimethoxysilane.
  • the silane coupling agent can modify the alumina particles by adding the alumina particles to the solvent.
  • the sound is dispersed, and the temperature is raised to 50 ° C to 60 ° C, then the silane coupling agent is added, and then the temperature is raised to 70 ° C for 4 h to 5 h.
  • the residue is filtered and retained, and the filter residue is dried and then modified alumina particles.
  • the solvent may be anhydrous ethanol or xylene.
  • the filter residue can be dried at a temperature of 120 ° C and the drying time can be 24 h.
  • the alumina particles are modified by a silane coupling agent to form an active chemical group such as an amino group or a hydroxyl group, and the alumina particles are chemically bonded to the liquid crystal epoxy resin through a reactive group such as an amino group or a hydroxyl group formed on the surface, thereby improving the interface.
  • the interaction reduces the thermal resistance of the interface and reduces the cluster phenomenon.
  • the reinforcing fibers are regularly arranged in the X-Y axis direction, have good thermal conductivity and mechanical properties, and improve the overall performance of the modified alumina composite.
  • the reinforcing fibers may be silicon carbide fibers.
  • the silicon carbide fiber is composed of 80 to 120 monofilaments, and each of the monofilaments has a diameter of 12 ⁇ m to 13 ⁇ m.
  • the silicon carbide fiber acts as a heat conduction bridge in the modified alumina composite material, and enhances the connection between the modified alumina particles and the modified alumina particles and the modified alumina particles and the silicon carbide fibers, to a large extent Forming a thermally conductive network structure or a thermally conductive chain.
  • each of the monofilaments of the silicon carbide fibers has a tensile strength of 2 GPa and a modulus of 150 GPa.
  • the liquid crystal epoxy resin has a large rigid biphenyl structure or a naphthalene structure with a large aspect ratio, and has a large improvement in thermal properties, mechanical properties and dielectric properties compared with ordinary epoxy resins or BT resins; for example, long diameter
  • the larger rigid structure can effectively suppress the scattering of phonons and increase the mean free path of phonons, so that its thermal conductivity is significantly improved.
  • the liquid crystal epoxy resin is selected from the group consisting of 3,3',5,5'-tetramethylbiphenyl diglycidyl ether, bisphenol A diglycidyl ether, 4,4'-dihydroxybiphenyl diglycidyl ether And at least one of 4,4'-dihydroxybinaphthyl diglycidyl ether.
  • the curing agent may be at least one of 4,4'-dihydroxybiphenyl, 4,4'-diaminobiphenyl, and 4,4'-diaminodiphenyl sulfone.
  • liquid crystal epoxy resin and the curing agent are in an equal stoichiometric ratio, that is, both the liquid crystal epoxy resin and the curing agent react exactly.
  • the sum of the mass of the modified alumina and the liquid crystal epoxy tree and the modified alumina composite was 7:10.
  • the promoter is at least one of triphenylphosphine, imidazole and chromium acetylacetonate.
  • the modified alumina composite material comprises modified alumina particles, reinforcing fibers and liquid crystal epoxy resin, and the modified alumina particles are obtained by modifying the alumina particles with a silane coupling agent.
  • the alumina particles are modified by a silane coupling agent to form an active chemical group such as an amino group or a hydroxyl group, and the alumina particles are chemically bonded to the liquid crystal epoxy resin through a reactive group such as an amino group or a hydroxyl group formed on the surface, thereby improving the interface.
  • the interaction reduces the thermal resistance of the interface and reduces the cluster phenomenon. Compared with traditional composite materials, this modified alumina composite is not prone to clustering.
  • a copper clad substrate includes a first electrode layer, a dielectric layer, and a second electrode layer which are sequentially laminated.
  • the material of the dielectric layer is the modified alumina composite described above.
  • the material of the first electrode layer is at least one of copper, brass, aluminum, and nickel.
  • the material of the second electrode layer is at least one of copper, brass, aluminum, and nickel.
  • the thickness of the first electrode layer is 10 ⁇ m to 35 ⁇ m
  • the thickness of the second electrode layer is 10 ⁇ m to 35 ⁇ m.
  • the method for preparing the above copper-clad substrate shown in FIG. 1 includes the following steps:
  • the organic solvent may be 2-butanone or acetone.
  • the modified alumina particles are obtained by modifying the alumina particles with a silane coupling agent.
  • the modified alumina particles may have a particle diameter of from 100 nm to 1000 nm.
  • the modified alumina particles have a particle size of 700 nm.
  • the silane coupling agent is ⁇ -aminopropyltriethoxysilane, ⁇ -(2,3-epoxypropoxy)propyltrimethoxysilane or ⁇ -methacryloxypropyltrimethoxysilane.
  • the silane coupling agent may modify the alumina particles by adding the alumina particles to the solvent and ultrasonically dispersing, heating to 50 ° C to 60 ° C, adding a silane coupling agent, and then heating to 70 ° C for 4 h to 5 h. After cooling, the filter residue is filtered and retained, and the filter residue is dried to be a modified alumina particle.
  • silane coupling agent The mass ratio to the alumina particles was 3:100.
  • the solvent may be anhydrous ethanol or xylene.
  • the filter residue can be dried at a temperature of 120 ° C and the drying time can be 24 h.
  • the alumina particles are modified by a silane coupling agent to form an active chemical group such as an amino group or a hydroxyl group, and the alumina particles are chemically bonded to the liquid crystal epoxy resin through a reactive group such as an amino group or a hydroxyl group formed on the surface, thereby improving the interface.
  • the interaction reduces the thermal resistance of the interface and reduces the cluster phenomenon.
  • the liquid crystal epoxy resin has a large rigid biphenyl structure or a naphthalene structure with a large aspect ratio, and has a large improvement in thermal properties, mechanical properties and dielectric properties compared with ordinary epoxy resins or BT resins; for example, long diameter
  • the larger rigid structure can effectively suppress the scattering of phonons and increase the mean free path of phonons, so that its thermal conductivity is significantly improved.
  • the liquid crystal epoxy resin is selected from the group consisting of 3,3',5,5'-tetramethylbiphenyl diglycidyl ether, bisphenol A diglycidyl ether, 4,4'-dihydroxybiphenyl diglycidyl ether And at least one of 4,4'-dihydroxybinaphthyl diglycidyl ether.
  • the curing agent may be at least one of 4,4'-dihydroxybiphenyl, 4,4'-diaminobiphenyl, and 4,4'-diaminodiphenyl sulfone.
  • liquid crystal epoxy resin and the curing agent are in an equal stoichiometric ratio, that is, both the liquid crystal epoxy resin and the curing agent react exactly.
  • the promoter is at least one of triphenylphosphine, imidazole and chromium acetylacetonate.
  • the material of the centrifugal film may be polyethylene terephthalate.
  • the centrifugal film of the polyethylene terephthalate material is easily peeled off when a semi-cured sheet is obtained because of its small surface tension.
  • the reinforcing fibers may be silicon carbide fibers.
  • the silicon carbide fiber is composed of 80 to 120 monofilaments, and each of the monofilaments has a diameter of 12 ⁇ m to 13 ⁇ m.
  • Silicon carbide fiber acts as a heat-conducting bridge in the modified alumina composite, enhancing the modified oxidation
  • the bonding between the aluminum particles and the modified alumina particles and the modified alumina particles and the silicon carbide fibers largely forms a thermally conductive network structure or a thermally conductive chain.
  • each of the monofilaments of the silicon carbide fibers has a tensile strength of 2 GPa and a modulus of 150 GPa.
  • the material of the first electrode layer is at least one of copper, brass, aluminum, and nickel.
  • the material of the second electrode layer is at least one of copper, brass, aluminum, and nickel.
  • the thickness of the first electrode layer is 10 ⁇ m to 35 ⁇ m
  • the thickness of the second electrode layer is 10 ⁇ m to 35 ⁇ m.
  • the curing operation may be: curing at 150 ° C, 180 ° C, 220 ° C for 2 h.
  • the dielectric layer of the copper-clad substrate prepared by the method for preparing the copper-clad substrate has a radial thermal conductivity of 0.701 to 1.004 W/m ⁇ K and an axial thermal conductivity of 1.325 to 1.526 W/m ⁇ K.
  • the transformation temperature is 170 to 180 °C.
  • the material of the dielectric layer of the copper-clad substrate prepared by the preparation method of the copper-clad substrate is a modified alumina composite material, and the modified alumina composite material comprises modified alumina particles, reinforcing fibers and liquid crystal epoxy resin, and is modified.
  • the alumina particles are obtained by modifying the alumina particles with a silane coupling agent.
  • the alumina particles are modified by a silane coupling agent to form an active chemical group such as an amino group or a hydroxyl group, and the alumina particles are chemically bonded to the liquid crystal epoxy resin through a reactive group such as an amino group or a hydroxyl group formed on the surface, thereby improving the interface.
  • the interaction reduces the thermal resistance of the interface and reduces the cluster phenomenon.
  • the ball mill selects a ball mill 50kg ball mill made by Meizhou Huafeng
  • the laser particle size analyzer is Malvern MS3000 laser particle size analyzer
  • the specific surface area analyzer is ASAP2020 specific surface area tester
  • the thermal conductivity tester is Hot Disk TPS2500s thermal analyzer.
  • the glass transition temperature tester is a TA Q20 differential scanning calorimeter
  • the scanning electron microscope is FEI's Nova Nano SEM 450.
  • the alumina particles were dried at 110 ° C for 4 h. After cooling to room temperature, 15.0 g of alumina particles having a particle diameter of 700 nm and 50 mL of xylene were weighed into a three-necked flask and ultrasonically dispersed for 10 min, and then placed in an oil bath, magnetically stirred. The solution was warmed to 90 °C. 1.0 g of the surface modifier ⁇ -aminopropyltriethoxysilane was added dropwise with a dropper, and the mixture was heated to 115 ° C after the dropwise addition, and magnetic stirring was continued for 6 hours.
  • the mixed solution was cooled, poured into a suction funnel while hot, and the sample obtained by suction filtration was washed with absolute ethanol for several times, and dried in a vacuum drying oven at 110 ° C for 12 h to obtain surface modification of ⁇ -aminopropyltriethoxysilane. Alumina.
  • Example 2 and 3 are SEM photographs of the alumina particles in Example 1 and the ⁇ -aminopropyltriethoxysilane-modified alumina particles prepared in Example 1 dispersed in an organic solvent, respectively.
  • alumina particles before modification tend to form clusters in an organic solvent, and the dispersibility is poor. Mainly because the alumina particles have a small specific surface area and a large surface energy, the alumina particles are easily combined into a block.
  • the ⁇ -aminopropyltriethoxysilane-modified alumina particles are substantially monodisperse and have little agglomeration. Mainly because the surface of the modified alumina particles is charged, the dispersion of the ⁇ -aminopropyltriethoxysilane-modified alumina particles is better due to the charge interaction.
  • the mixed solution prepared above was applied by a bar coating method to silicon carbide fibers which were regularly arranged in a crosswise arrangement in the X-Y plane. It was baked in a blast oven at 130 ° C for 120 minutes to volatilize the solvent to obtain a prepreg.
  • the total mass percentage of the alumina and liquid crystal epoxy composites was 70%.
  • FIG. 4 is an electron micrograph of a liquid crystal epoxy resin coated longitudinally arranged silicon carbide fiber. As can be seen from FIG. 4, the modified alumina particles are uniformly dispersed in the liquid crystal epoxy resin, and the modified alumina particles are closely adhered. On the surface of silicon carbide fibers.
  • FIG. 5 is an electron micrograph of a silicon carbide fiber coated with a liquid crystal epoxy resin in a radial arrangement.
  • the liquid crystal epoxy resin has a good overall coating effect and has fewer defects, and the silicon carbide fiber fully functions.
  • the function of the heat-conducting bridge enhances the connection between the modified alumina particles and the modified alumina particles and between the modified alumina particles and the silicon carbide fibers, and forms a heat-conductive network structure or a heat-conducting chain to a large extent.
  • the silicon carbide fibers of the two are closely adhered, and placed between the first electrode layer and the second electrode layer, and hot pressed at 150 ° C and a pressure of 5 kgf / cm 2 in a vacuum press. After 3 hours, finally, in a blast oven, curing at 150 ° C, 180 ° C, 220 ° C for 2 h, respectively, to obtain a copper-clad substrate.
  • the prepared copper-clad substrate comprises a first electrode layer, a dielectric layer and a second electrode layer which are sequentially stacked, wherein the first electrode layer and the second electrode layer are both copper foil sheets having a thickness of 40 ⁇ m, and the dielectric layer is two prepregs. Composition, the prepreg has a thickness of 500 microns.
  • the copper-clad substrate prepared in Example 1 had a radial thermal conductivity of 0.701 W/m ⁇ K, an axial thermal conductivity of 1.325 W/m ⁇ K, and a glass transition temperature of 175° C.
  • the preparation method is basically the same as that in the first embodiment, except that the curing agent used in the step (2) is 4,4'-dihydroxybiphenyl, stirred and mixed uniformly at 130 ° C, and maintained at a temperature of 130 ° C for 30 min to obtain amber viscous.
  • the curing agent used in the step (2) is 4,4'-dihydroxybiphenyl, stirred and mixed uniformly at 130 ° C, and maintained at a temperature of 130 ° C for 30 min to obtain amber viscous.
  • a transparent epoxy resin composite is 4,4'-dihydroxybiphenyl
  • the prepared copper-clad substrate comprises a first electrode layer, a dielectric layer and a second electrode layer which are sequentially laminated, wherein the first electrode layer and the second electrode layer are both copper foil sheets having a thickness of 40 ⁇ m, and the dielectric layer is composed of two prepregs Composition, thickness is 500 microns.
  • the substrate material had a radial thermal conductivity of 0.876 W/m ⁇ K, an axial thermal conductivity of 1.358 W/m ⁇ K, and a glass transition temperature of 130 ° C.
  • the preparation method is basically the same as that of Example 1, except that step (2) adds 5.60 g (55 parts) of ⁇ -aminopropyltriethoxysilane-containing alumina and 2.40 g of epoxy resin system to 4.50 g.
  • the 2-butanone solvent was stirred by an ultrasonic vibration method for 2 hours, and uniformly mixed to obtain an alumina composite material.
  • the prepared copper-clad substrate comprises a first electrode layer, a dielectric layer and a second electrode layer which are sequentially stacked, wherein the first electrode layer and the second electrode layer are both copper foil sheets having a thickness of 40 ⁇ m, and the dielectric layer is composed of two prepregs. Composition, thickness is 500 microns.
  • the substrate material had a radial thermal conductivity of 1.004 W/m ⁇ K, an axial thermal conductivity of 1.526 W/m ⁇ K, and a glass transition temperature of 180 ° C.
  • the preparation method was the same as in Example 1, except that the step (2) was applied to the glass fiber cloth.
  • the prepared copper-clad substrate comprises a first electrode layer, a dielectric layer and a second electrode layer which are sequentially stacked, wherein the first electrode layer and the second electrode layer are both copper foil sheets having a thickness of 40 ⁇ m, and the dielectric layer is composed of two prepregs. The thickness is 100 microns.
  • the substrate material had a radial thermal conductivity of 0.777 W/m ⁇ K, an axial thermal conductivity of 0.803 W/m ⁇ K, and a glass transition temperature of 175 ° C.
  • the preparation method was the same as in Example 2 except that the same amount of unmodified alumina was added in the step (2).
  • the prepared copper-clad substrate comprises a first electrode layer, a dielectric layer and a second electrode layer which are sequentially stacked, wherein the first electrode layer and the second electrode layer are both copper foil sheets having a thickness of 40 ⁇ m, and the dielectric layer is composed of two prepregs. Composition, thickness is 500 microns.
  • the substrate material has a radial thermal conductivity of 0.592 W/m ⁇ K, and the axis guide The thermal coefficient was 0.888 W/m ⁇ K and the glass transition temperature was 175 °C.

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Abstract

本发明公开了一种改性氧化铝复合材料，按照质量分数包括35份～55份的改性氧化铝颗粒、25份～35份的增强纤维、15份～35份的液晶环氧树脂、10份～21份的固化剂以及0.1份～1份的促进剂，改性氧化铝颗粒为硅烷偶联剂改性氧化铝颗粒得到。这种改性氧化铝复合材料，包括改性氧化铝颗粒、增强纤维和液晶环氧树脂。氧化铝颗粒经过硅烷偶联剂改性后表面形成氨基、羟基等活性化学基团，氧化铝颗粒通过表面形成的氨基、羟基等活性基团与液晶环氧树脂之间通过化学键连接，提高了界面的相互作用，减小了界面热阻，减少了团簇现象。本发明还公开了采用上述改性氧化铝复合材料的覆铜基板及其制备方法。

Description

改性氧化铝复合材料、覆铜基板及其制备方法 技术领域
本发明涉及覆铜基板的制备领域，特别是涉及一种改性氧化铝复合材料、采用该改性氧化铝复合材料的覆铜基板及其制备方法。
背景技术
覆铜基板是将电子玻纤布或其他增强材料浸以树脂，一面或二面覆以铜箔并经热压而制成的一种板状材料。覆铜基板主要是为芯片提供导热、绝缘和支撑三个方面的功能，是制造印刷线路板(PCB)的关键原材料。近年来，电子产品正朝着便携式、小型化、轻量化和多功能方向发展，这种市场需求对覆铜基板提出了更高的要求。
到目前为止，氧化铝是微电子工业中最常用的基板材料，因为在机械、热、电性能上它优于常用于基板材料中的陶瓷颗粒二氧化硅。氧化铝原料丰富，价格低廉，热稳定性高，氧化铝在高达1925℃的氧化和还原气氛中都是稳定的。氧化铝的理想导热系数达到30W/m·K，将氧化铝颗粒均匀地添加到覆铜基板中，可以极大地提高基板材料的机械性能和热性能。
然而，氧化铝颗粒比表面积较大、表面能较高，从而使得氧化铝颗粒很容易聚集成团，而且由于氧化铝与聚合物之间作用力较低，氧化铝在聚合物基体中更加难以均匀分布，传统的含有氧化铝颗粒的覆铜基板的容易出现团簇现象。
发明内容
基于此，有必要提供一种不容易出现团簇现象的覆铜基板以及制备方法，以及可以用于该覆铜基板改性氧化铝复合材料。
一种改性氧化铝复合材料，按照质量分数包括35份～55份的改性氧化铝颗粒、25份～35份的增强纤维、15份～35份的液晶环氧树脂、10份～21份的固化 剂以及0.1份～1份的促进剂；
所述改性氧化铝颗粒为硅烷偶联剂改性氧化铝颗粒得到，所述改性氧化铝颗粒的粒径为100nm～1000nm。
在一个实施例中，所述硅烷偶联剂改性所述氧化铝颗粒的过程如下：将所述氧化铝颗粒加入到溶剂中超声分散，升温至50℃～60℃后加入所述硅烷偶联剂，接着搅拌升温至70℃反应4h～5h，冷却后过滤并保留滤渣，所述滤渣干燥后即为所述改性氧化铝颗粒，其中，所述硅烷偶联剂与所述氧化铝颗粒的质量比为3∶100。
在一个实施例中，所述硅烷偶联剂为γ-氨丙基三乙氧基硅烷、γ-(2，3-环氧丙氧)丙基三甲氧基硅烷或γ-甲基丙烯酰氧基丙基三甲氧基硅烷。
在一个实施例中，所述增强纤维按照X-Y轴方向规则交叉排列。
在一个实施例中，所述增强纤维为碳化硅纤维。
在一个实施例中，所述碳化硅纤维由80根～120根单丝组成，每根所述单丝的直径为12μm～13μm。
在一个实施例中，所述液晶环氧树脂为3，3’，5，5’-四甲基联苯二缩水甘油醚、双酚A二缩水甘油醚、4，4’-二羟基联苯二缩水甘油醚和4，4’-二羟基联萘基二缩水甘油醚中的至少一种。
在一个实施例中，所述固化剂为4，4’-二羟基联苯、4，4’-二氨基联苯和4，4’-二氨基二苯砜中的至少一种。
在一个实施例中，所述液晶环氧树脂与所述固化剂为等化学计量比。
在一个实施例中，所述促进剂为三苯基膦、咪唑和乙酰丙酮铬中的至少一种。
一种覆铜基板，包括依次层叠的第一电极层、电介质层和第二电极层；其特征在于，所述电介质层的材料为上述的改性氧化铝复合材料。
在一个实施例中，所述第一电极层的材料为铜、黄铜、铝和镍中的至少一种，所述第二电极层为铜、黄铜、铝和镍中的至少一种。
一种覆铜基板的制备方法，包括如下步骤：
按照质量分数将35份～55份的改性氧化铝颗粒、15份～35份的液晶环氧树脂、10份～21份的固化剂以及0.1份～1份的促进剂溶解在有机溶剂中，超声0.5h～2h后得到混合溶液；
按照质量分数将25份～35份的增强纤维排列在离心膜上，接着将所述混合溶液涂覆在所述增强纤维上并在60℃～150℃下烘烤10min～90min，得到半固化板；以及
将所述半固化板置于第一电极层和第二电极层之间，接着在120℃～200℃、5kgf/cm2～30kgf/cm2的压力下热压4h～10h，最后固化，得到所述覆铜基板。
在一个实施例中，所述改性氧化铝颗粒的制备过程如下：将所述氧化铝颗粒加入到溶剂中超声分散，升温至50℃～60℃后加入所述硅烷偶联剂，接着搅拌升温至70℃反应4h～5h，冷却后过滤并保留滤渣，所述滤渣干燥后即为所述改性氧化铝颗粒，其中，所述硅烷偶联剂与所述氧化铝颗粒的质量比为3∶100。
在一个实施例中，所述硅烷偶联剂为γ-氨丙基三乙氧基硅烷、γ-(2，3-环氧丙氧)丙基三甲氧基硅烷或γ-甲基丙烯酰氧基丙基三甲氧基硅烷，所述硅烷偶联剂与所述氧化铝颗粒的质量比为3∶100。
在一个实施例中，将25份～35份的增强纤维排列在离心膜上的操作为：将25份～35份的所述增强纤维按照X-Y轴方向规则交叉排列在所述离心膜上，所述增强纤维为碳化硅纤维。
在一个实施例中，所述碳化硅纤维由80根～120根单丝组成，每根所述单丝的直径为12μm～13μm。
在一个实施例中，所述液晶环氧树脂为3，3’，5，5’-四甲基联苯二缩水甘油醚、双酚A二缩水甘油醚、4，4’-二羟基联苯二缩水甘油醚和4，4’-二羟基联萘基二缩水甘油醚中的至少一种；
所述固化剂为4，4’-二羟基联苯、4，4’-二氨基联苯和4，4’-二氨基二苯砜中的至少一种；
所述液晶环氧树脂与所述固化剂为等化学计量比。
在一个实施例中，所述离心膜为的材料为聚对苯二甲酸乙二醇酯。
这种改性氧化铝复合材料，包括改性氧化铝颗粒、增强纤维和液晶环氧树脂，改性氧化铝颗粒为硅烷偶联剂改性氧化铝颗粒得到。氧化铝颗粒经过硅烷偶联剂改性后表面形成氨基、羟基等活性化学基团，氧化铝颗粒通过表面形成的氨基、羟基等活性基团与液晶环氧树脂之间通过化学键连接，提高了界面的相互作用，减小了界面热阻，减少了团簇现象。相对于传统的复合材料，这种改性氧化铝复合材料不容易出现团簇现象。
附图说明
图1为一实施方式的覆铜基板的制造方法的流程图；
图2为实施例1中的氧化铝颗粒在有机溶剂中分散的SEM照片；
图3为实施例1制得的γ-氨丙基三乙氧基硅烷改性的氧化铝颗粒在有机溶剂中分散的SEM照片；
图4为实施例1制得的半固化片的截面电镜图；
图5为实施例1制得的半固化片的截面电镜图。
具体实施方式
下面主要结合附图及具体实施例对铁氧体粉体的制造方法作进一步详细的说明。
一实施方式的改性氧化铝复合材料，按照质量分数包括35份～55份的改性氧化铝颗粒、25份～35份的增强纤维、15份～35份的液晶环氧树脂、10份～21份的固化剂以及0.1份～1份的促进剂。
改性氧化铝颗粒为硅烷偶联剂改性氧化铝颗粒得到。改性氧化铝颗粒的粒径可以为100nm～1000nm。
在一个较优的实施例中，改性氧化铝颗粒的粒径为700nm。
硅烷偶联剂为γ-氨丙基三乙氧基硅烷、γ-(2，3-环氧丙氧)丙基三甲氧基硅烷或γ-甲基丙烯酰氧基丙基三甲氧基硅烷。
硅烷偶联剂改性氧化铝颗粒的过程可以为：将氧化铝颗粒加入到溶剂中超 声分散，升温至50℃～60℃后加入硅烷偶联剂，接着搅拌升温至70℃反应4h～5h，冷却后过滤并保留滤渣，滤渣干燥后即为改性氧化铝颗粒。其中，硅烷偶联剂与氧化铝颗粒的质量比为3∶100。溶剂可以为无水乙醇或二甲苯。滤渣干燥的温度可以为120℃，干燥的时间可以为24h。
氧化铝颗粒经过硅烷偶联剂改性后表面形成氨基、羟基等活性化学基团，氧化铝颗粒通过表面形成的氨基、羟基等活性基团与液晶环氧树脂之间通过化学键连接，提高了界面的相互作用，减小了界面热阻，减少了团簇现象。
增强纤维按照X-Y轴方向规则交叉排列，具有很好的导热性能和力学性能，提高改性氧化铝复合材料的整体性能。
增强纤维可以为碳化硅纤维。碳化硅纤维由80根～120根单丝组成，每根单丝的直径为12μm～13μm。
碳化硅纤维在改性氧化铝复合材料中充当导热桥的作用，增强了改性氧化铝颗粒和改性氧化铝颗粒以及改性氧化铝颗粒和碳化硅纤维之间的连接作用，在很大程度上形成导热网络结构或者导热链。
本实施方式中，碳化硅纤维的每根单丝的拉伸强度为2GPa，模量为150GPa。
液晶环氧树脂选择具有较多的长径比大的刚性联苯结构或萘结构，较普通环氧树脂或者BT树脂在热性能、力学性能和介电性能方面有较大的提高；比如长径比大的刚性结构可以有效的抑制声子的散射，增加声子的平均自由程，从而使其导热性能显著提高。
具体的，液晶环氧树脂选自3，3’，5，5’-四甲基联苯二缩水甘油醚、双酚A二缩水甘油醚、4，4’-二羟基联苯二缩水甘油醚和4，4’-二羟基联萘基二缩水甘油醚中的至少一种。
固化剂可以为4，4’-二羟基联苯、4，4’-二氨基联苯和4，4’-二氨基二苯砜中的至少一种。
本实施方式中，液晶环氧树脂与固化剂为等化学计量比，即，液晶环氧树脂与固化剂二者均恰好完全反应。
本实施方式中，改性氧化铝和液晶环氧树的质量之和与改性氧化铝复合材 料的总质量的比例为7∶10。
促进剂为三苯基膦、咪唑和乙酰丙酮铬中的至少一种。
这种改性氧化铝复合材料，包括改性氧化铝颗粒、增强纤维和液晶环氧树脂，改性氧化铝颗粒为硅烷偶联剂改性氧化铝颗粒得到。氧化铝颗粒经过硅烷偶联剂改性后表面形成氨基、羟基等活性化学基团，氧化铝颗粒通过表面形成的氨基、羟基等活性基团与液晶环氧树脂之间通过化学键连接，提高了界面的相互作用，减小了界面热阻，减少了团簇现象。相对于传统的复合材料，这种改性氧化铝复合材料不容易出现团簇现象。
一实施方式的覆铜基板，包括依次层叠的第一电极层、电介质层和第二电极层。
电介质层的材料为上述的改性氧化铝复合材料。
第一电极层的材料为铜、黄铜、铝和镍中的至少一种。第二电极层的材料为铜、黄铜、铝和镍中的至少一种。
第一电极层的厚度为10μm～35μm，第二电极层的厚度为10μm～35μm。
如图1所示的上述覆铜基板的制备方法，包括如下步骤：
S10、按照质量分数将35份～55份的改性氧化铝颗粒、15份～35份的液晶环氧树脂、10份～21份的固化剂以及0.1份～1份的促进剂溶解在有机溶剂中，超声0.5h～2h后得到混合溶液。
有机溶剂可以为2-丁酮或丙酮。
改性氧化铝颗粒为硅烷偶联剂改性氧化铝颗粒得到。改性氧化铝颗粒的粒径可以为100nm～1000nm。
在一个较优的实施例中，改性氧化铝颗粒的粒径为700nm。
硅烷偶联剂为γ-氨丙基三乙氧基硅烷、γ-(2，3-环氧丙氧)丙基三甲氧基硅烷或γ-甲基丙烯酰氧基丙基三甲氧基硅烷。
硅烷偶联剂改性氧化铝颗粒的过程可以为：将氧化铝颗粒加入到溶剂中超声分散，升温至50℃～60℃后加入硅烷偶联剂，接着搅拌升温至70℃反应4h～5h，冷却后过滤并保留滤渣，滤渣干燥后即为改性氧化铝颗粒。其中，硅烷偶联剂 与氧化铝颗粒的质量比为3∶100。溶剂可以为无水乙醇或二甲苯。滤渣干燥的温度可以为120℃，干燥的时间可以为24h。
氧化铝颗粒经过硅烷偶联剂改性后表面形成氨基、羟基等活性化学基团，氧化铝颗粒通过表面形成的氨基、羟基等活性基团与液晶环氧树脂之间通过化学键连接，提高了界面的相互作用，减小了界面热阻，减少了团簇现象。
液晶环氧树脂选择具有较多的长径比大的刚性联苯结构或萘结构，较普通环氧树脂或者BT树脂在热性能、力学性能和介电性能方面有较大的提高；比如长径比大的刚性结构可以有效的抑制声子的散射，增加声子的平均自由程，从而使其导热性能显著提高。
具体的，液晶环氧树脂选自3，3’，5，5’-四甲基联苯二缩水甘油醚、双酚A二缩水甘油醚、4，4’-二羟基联苯二缩水甘油醚和4，4’-二羟基联萘基二缩水甘油醚中的至少一种。
固化剂可以为4，4’-二羟基联苯、4，4’-二氨基联苯和4，4’-二氨基二苯砜中的至少一种。
本实施方式中，液晶环氧树脂与固化剂为等化学计量比，即，液晶环氧树脂与固化剂二者均恰好完全反应。
促进剂为三苯基膦、咪唑和乙酰丙酮铬的至少一种。
S20、按照质量分数将25份～35份的增强纤维排列在离心膜上，接着将S10得到的混合溶液涂覆在增强纤维上并在60℃～150℃下烘烤10min～90min，待冷却至室温后将离心膜剥离得到半固化板。
离心膜为的材料可以为聚对苯二甲酸乙二醇酯。聚对苯二甲酸乙二醇酯材料的离心膜由于其表面张力较小，在得到半固化板时易剥离。
具体的，S20中，将25份～35份的增强纤维按照X-Y轴方向规则交叉排列在离心膜上。
增强纤维可以为碳化硅纤维。碳化硅纤维由80根～120根单丝组成，每根单丝的直径为12μm～13μm。
碳化硅纤维在改性氧化铝复合材料中充当导热桥的作用，增强了改性氧化 铝颗粒和改性氧化铝颗粒以及改性氧化铝颗粒和碳化硅纤维之间的连接作用，在很大程度上形成导热网络结构或者导热链。
本实施方式中，碳化硅纤维的每根单丝的拉伸强度为2GPa，模量为150GPa。
S30、将S20得到的半固化板置于第一电极层和第二电极层之间，接着在120℃～200℃、5kgf/cm2～30kgf/cm2的压力下热压4h～10h，最后固化，得到覆铜基板。
第一电极层的材料为铜、黄铜、铝和镍中的至少一种。第二电极层的材料为铜、黄铜、铝和镍中的至少一种。
第一电极层的厚度为10μm～35μm，第二电极层的厚度为10μm～35μm。
固化的操作可以为：分别在150℃、180℃、220℃下固化2h。
经过测试，这种覆铜基板的制备方法制得的覆铜基板的电介质层的径向导热系数为0.701～1.004W/m·K，轴向导热系数为1.325～1.526W/m·K，玻璃化转变温度为170～180℃。
这种覆铜基板的制备方法制得的覆铜基板的电介质层的材料为改性氧化铝复合材料，改性氧化铝复合材料包括改性氧化铝颗粒、增强纤维和液晶环氧树脂，改性氧化铝颗粒为硅烷偶联剂改性氧化铝颗粒得到。氧化铝颗粒经过硅烷偶联剂改性后表面形成氨基、羟基等活性化学基团，氧化铝颗粒通过表面形成的氨基、羟基等活性基团与液晶环氧树脂之间通过化学键连接，提高了界面的相互作用，减小了界面热阻，减少了团簇现象。
下面为具体实施例。实施例中，球磨选择梅州华丰制作的球磨机50kg级球磨机，激光粒度分析仪为马尔文MS3000激光粒度仪，比表面积分析仪为ASAP2020比表面积测试仪，导热系数测试仪为Hot Disk TPS2500s热分析仪，玻璃化转变温度测试仪为TA Q20差示扫描量热测试仪，扫描电镜为FEI公司的Nova Nano SEM 450。
实施例1
(1)制备γ-氨丙基三乙氧基硅烷改性的氧化铝。
首先将氧化铝颗粒在110℃下干燥4h，待冷却至室温后称取15.0g粒径为700nm的氧化铝颗粒、50mL二甲苯加入到三口烧瓶中超声分散10min后放入油浴锅，磁力搅拌溶液并升温至90℃。用滴管逐滴加入1.0g表面改性剂γ-氨丙基三乙氧基硅烷，滴加后升温至115℃，保持磁力搅拌，反应6h。
将混合溶液冷却，趁热倒入抽滤漏斗，抽滤得到的样品用无水乙醇多次洗涤，放入真空干燥箱110℃干燥12h，得到γ-氨丙基三乙氧基硅烷表面改性的氧化铝。
图2和图3分别为实施例1中的氧化铝颗粒与实施例1制得的γ-氨丙基三乙氧基硅烷改性的氧化铝颗粒在有机溶剂中分散的SEM照片。
由图2可以看出，改性前的氧化铝颗粒在有机溶剂中易形成团簇，分散性较差。主要因为氧化铝颗粒比表面积较小，表面能很大，氧化铝颗粒之间容易结合成块。
由图3可以看出，γ-氨丙基三乙氧基硅烷改性的氧化铝颗粒基本呈现单分散，很少有团聚。主要因为改性后的氧化铝颗粒表面带有电荷，由于电荷的相互作用是γ-氨丙基三乙氧基硅烷改性的氧化铝颗粒分散性较好。
(2)制备半固化片。
将2.60g 3，3’，5，5’-四甲基联苯二缩水甘油醚、1.40g 4，4’-二氨基二苯砜以及20.00mg三苯基膦在180℃搅拌混合均匀，维持温度180℃反应30min，得琥珀色粘稠状透明的环氧树脂复合物。
将制得的4.00g环氧树脂复合物、4.00g经γ-氨丙基三乙氧基硅烷表面改性的氧化铝加入到4.50g的2-丁酮溶剂中，通过超声波震荡方法搅拌2h，混合均匀，得到混合溶液。
将上述制备的混合溶液采用棒式涂布方式涂布在在X-Y平面内呈规则状交叉排列的碳化硅纤维上。放入鼓风烘箱中130℃烘烤120分钟，使溶剂挥发，得到半固化片。半固化片中，氧化铝和液晶环氧树脂复合材料的总质量百分数为70％。
图4和图5分别为实施例1制得的半固化片的截面电镜图。
图4为液晶环氧树脂包覆纵向排布的碳化硅纤维的电镜图，由图4可看出，改性氧化铝颗粒均匀分散在液晶环氧树脂中，同时改性氧化铝颗粒紧密的附着在碳化硅纤维的表面。
图5为液晶环氧树脂包覆径向排布的碳化硅纤维的电镜图，由图5可看出，液晶环氧树脂整体包覆效果较好，存在缺陷较少，碳化硅纤维充分的充当了导热桥的作用，增强了改性氧化铝颗粒和改性氧化铝颗粒之间以及改性氧化铝颗粒和碳化硅纤维之间的连接作用，在很大程度上形成导热网络结构或者导热链。
(3)制备覆铜基板。
首先用浓度为15wt％的盐酸溶液清洗两个厚度为40微米的铜箔片，然后再将两个铜箔片置于丙酮中超声清洗10min后置于无水乙醇中超声清洗10min，烘箱中60℃烘干，得到洁净、干燥的第一电极层和第二电极层。
将两个半固化片重叠后二者的碳化硅纤维贴紧，将其置于第一电极层和第二电极层之间，于真空压机中，在150℃、5kgf/cm2的压力下热压3小时，最后在鼓风烘箱中，分别在150℃、180℃、220℃下固化2h，制得覆铜基板。
制得的覆铜基板包括依次层叠的第一电极层、电介质层和第二电极层，其中第一电极层和第二电极层均为厚度为40微米的铜箔片，电介质层为两片半固化片所组成，半固化片厚度为500微米。
测试后发现，实施例1制备得到的覆铜基板的径向导热系数为0.701W/m·K，轴向导热系数为1.325W/m·K，玻璃化转变温度为175℃。
实施例2
制备方法与实施例1基本相同，区别仅在于：步骤(2)使用的固化剂为4，4’-二羟基联苯，130℃搅拌混合均匀，维持温度130℃反应30min，得琥珀色粘稠状透明的环氧树脂复合物。
制备得到的覆铜基板包括依次层叠的第一电极层、电介质层和第二电极层，其中第一电极层和第二电极层均为厚度为40微米的铜箔片，电介质层由2张半固化片组成，厚度为500微米。
测试后发现，基板材料径向导热系数0.876W/m·K，轴向导热系数为1.358W/m·K，玻璃化转变温度为130℃。
实施例3
制备方法与实施例1基本相同，区别仅在于：步骤(2)将5.60g(55份)经γ-氨丙基三乙氧基硅烷的氧化铝和2.40g环氧树脂体系加入到4.50g的2-丁酮溶剂中，通过超声波震荡方法搅拌2h，混合均匀，得到氧化铝复合材料。
制备得到的覆铜基板包括依次层叠的第一电极层、电介质层和第二电极层，其中第一电极层和第二电极层均为厚度为40微米的铜箔片，电介质层由2片半固化片组成，厚度为500微米。
测试后发现，基板材料径向导热系数为1.004W/m·K，轴向导热系数为1.526W/m·K，玻璃化转变温度为180℃。
对比例1
制备方法与实施例1相同，区别仅在于：步骤(2)中涂覆在玻璃纤维布上。
制备得到的覆铜基板包括依次层叠的第一电极层、电介质和第二电极层，其中第一电极层和第二电极层均为厚度为40微米的铜箔片，电介质层由2片半固化片组成，厚度为100微米。
测试后发现，基板材料径向导热系数为0.777W/m·K，轴向导热系数为0.803W/m·K，玻璃化转变温度为175℃。
对比例2
制备方法与实施例2相同，区别仅在于：步骤(2)中添加相同量的未改性的氧化铝。
制备得到的覆铜基板包括依次层叠的第一电极层、电介质层和第二电极层，其中第一电极层和第二电极层均为厚度为40微米的铜箔片，电介质层由2片半固化片组成，厚度为500微米。基板材料径向导热系数0.592W/m·K，轴向导 热系数为0.888W/m·K，玻璃化转变温度为175℃。
以上所述实施例仅表达了本发明的几种实施方式，其描述较为具体和详细，但并不能因此而理解为对本发明专利范围的限制。应当指出的是，对于本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进，这些都属于本发明的保护范围。因此，本发明专利的保护范围应以所附权利要求为准。

Claims (19)

  1. 一种改性氧化铝复合材料，其特征在于，按照质量分数包括35份～55份的改性氧化铝颗粒、25份～35份的增强纤维、15份～35份的液晶环氧树脂、10份～21份的固化剂以及0.1份～1份的促进剂；
    所述改性氧化铝颗粒为硅烷偶联剂改性氧化铝颗粒得到，所述改性氧化铝颗粒的粒径为100nm～1000nm。
  2. 如权利要求1所述的改性氧化铝复合材料，其特征在于，所述硅烷偶联剂改性所述氧化铝颗粒的过程如下：将所述氧化铝颗粒加入到溶剂中超声分散，升温至50℃～60℃后加入所述硅烷偶联剂，接着搅拌升温至70℃反应4h～5h，冷却后过滤并保留滤渣，所述滤渣干燥后即为所述改性氧化铝颗粒，其中，所述硅烷偶联剂与所述氧化铝颗粒的质量比为3∶100。
  3. 如权利要求1或2所述的改性氧化铝复合材料，其特征在于，所述硅烷偶联剂为γ-氨丙基三乙氧基硅烷、γ-(2，3-环氧丙氧)丙基三甲氧基硅烷或γ-甲基丙烯酰氧基丙基三甲氧基硅烷。
  4. 如权利要求1所述的改性氧化铝复合材料，其特征在于，所述增强纤维按照X-Y轴方向规则交叉排列。
  5. 如权利要求1或4所述的改性氧化铝复合材料，其特征在于，所述增强纤维为碳化硅纤维。
  6. 如权利要求5所述的改性氧化铝复合材料，其特征在于，所述碳化硅纤维由80根～120根单丝组成，每根所述单丝的直径为12μm～13μm。
  7. 如权利要求1所述的改性氧化铝复合材料，其特征在于，所述液晶环氧树脂为3，3’，5，5’-四甲基联苯二缩水甘油醚、双酚A二缩水甘油醚、4，4’-二羟基联苯二缩水甘油醚和4，4’-二羟基联萘基二缩水甘油醚中的至少一种。
  8. 如权利要求1所述的改性氧化铝复合材料，其特征在于，所述固化剂为4，4’-二羟基联苯、4，4’-二氨基联苯和4，4’-二氨基二苯砜中的至少一种。
  9. 如权利要求1、7或8所述的改性氧化铝复合材料，其特征在于，所述液晶环氧树脂与所述固化剂为等化学计量比。
  10. 如权利要求1所述的改性氧化铝复合材料，其特征在于，所述促进剂为三苯基膦、咪唑和乙酰丙酮铬中的至少一种。
  11. 一种覆铜基板，包括依次层叠的第一电极层、电介质层和第二电极层；其特征在于，所述电介质层的材料为如权利要求1～10中任一项所述的改性氧化铝复合材料。
  12. 如权利要求11所述的覆铜基板，其特征在于，所述第一电极层的材料为铜、黄铜、铝和镍中的至少一种，所述第二电极层为铜、黄铜、铝和镍中的至少一种。
  13. 一种覆铜基板的制备方法，其特征在于，包括如下步骤：
    按照质量分数将35份～55份的改性氧化铝颗粒、15份～35份的液晶环氧树脂、10份～21份的固化剂以及0.1份～1份的促进剂溶解在有机溶剂中，超声0.5h～2h后得到混合溶液；
    按照质量分数将25份～35份的增强纤维排列在离心膜上，接着将所述混合溶液涂覆在所述增强纤维上并在60℃～150℃下烘烤10min～90min，待冷却至室温后将所述离心膜剥离得到半固化板；
    将所述半固化板置于第一电极层和第二电极层之间，接着在120℃～200℃、5kgf/cm2～30kgf/cm2的压力下热压4h～10h，最后固化，得到所述覆铜基板。
  14. 如权利要求13所述的覆铜基板的制备方法，其特征在于，所述改性氧化铝颗粒的制备过程如下：将所述氧化铝颗粒加入到溶剂中超声分散，升温至50℃～60℃后加入所述硅烷偶联剂，接着搅拌升温至70℃反应4h～5h，冷却后过滤并保留滤渣，所述滤渣干燥后即为所述改性氧化铝颗粒，其中，所述硅烷偶联剂与所述氧化铝颗粒的质量比为3∶100。
  15. 如权利要求14所述的覆铜基板的制备方法，其特征在于，所述硅烷偶联剂为γ-氨丙基三乙氧基硅烷、γ-(2，3-环氧丙氧)丙基三甲氧基硅烷或γ-甲基丙烯酰氧基丙基三甲氧基硅烷，所述硅烷偶联剂与所述氧化铝颗粒的质量比为3∶100。
  16. 如权利要求13所述的覆铜基板的制备方法，其特征在于，将25份～35 份的增强纤维排列在离心膜上的操作为：将25份～35份的所述增强纤维按照X-Y轴方向规则交叉排列在所述离心膜上，所述增强纤维为碳化硅纤维。
  17. 如权利要求16所述的覆铜基板的制备方法，其特征在于，所述碳化硅纤维由80根～120根单丝组成，每根所述单丝的直径为12μm～13μm。
  18. 如权利要求13所述的覆铜基板的制备方法，其特征在于，所述液晶环氧树脂为3，3’，5，5’-四甲基联苯二缩水甘油醚、双酚A二缩水甘油醚、4，4’-二羟基联苯二缩水甘油醚和4，4’-二羟基联萘基二缩水甘油醚中的至少一种；
    所述固化剂为4，4’-二羟基联苯、4，4’-二氨基联苯和4，4’-二氨基二苯砜中的至少一种；
    所述液晶环氧树脂与所述固化剂为等化学计量比。
  19. 如权利要求13所述的覆铜基板的制备方法，其特征在于，所述离心膜的材料为聚对苯二甲酸乙二醇酯。
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