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WO2024130787A1 - 用于印刷毛细结构的铜浆及其制备方法 - Google Patents

用于印刷毛细结构的铜浆及其制备方法 Download PDF

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Publication number
WO2024130787A1
WO2024130787A1 PCT/CN2022/144334 CN2022144334W WO2024130787A1 WO 2024130787 A1 WO2024130787 A1 WO 2024130787A1 CN 2022144334 W CN2022144334 W CN 2022144334W WO 2024130787 A1 WO2024130787 A1 WO 2024130787A1
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Prior art keywords
copper
printing
copper paste
mixed
polymer
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Ceased
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PCT/CN2022/144334
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English (en)
French (fr)
Inventor
张波
黄国创
王和志
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AAC Technologies Holdings Nanjing Co Ltd
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AAC Technologies Holdings Nanjing Co Ltd
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Priority to US18/338,378 priority Critical patent/US20240198418A1/en
Publication of WO2024130787A1 publication Critical patent/WO2024130787A1/zh
Anticipated expiration legal-status Critical
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K7/00—Constructional details common to different types of electric apparatus
    • H05K7/20—Modifications to facilitate cooling, ventilating, or heating

Definitions

  • the present invention relates to the technical field of temperature equalizing plates, and in particular to a copper paste for printing a capillary structure and a preparation method thereof.
  • the high-frequency and high-speed development of electronic components and integrated circuit technology will cause electronic components to generate a lot of heat during operation.
  • the heat flux density of computer CPU during operation has reached 60-100 W/cm2, and even as high as 103 W/cm2 in semiconductor lasers.
  • radiators are usually installed on electronic components to dissipate heat.
  • the current mainstream design is to install a heat spreader with good thermal conductivity between the radiator and the electronic components. The function of the heat spreader is to evenly distribute the heat of the heat-generating electronic components and then dissipate it through the radiator.
  • the heat spreader is a heat-conducting component that relies on the phase change of the working fluid inside to achieve rapid heat transfer. It mainly includes upper and lower cover plates or metal tubes, sealing heads, wicks and heat transfer media. Among them, the capillary structure of the wick directly affects the performance of the heat spreader. The capillary structure requires strong capillary force and small water flow resistance.
  • thermoelectric board There are many types of liquid-absorbing cores with capillary structures in the temperature-averaging board, such as foam copper, copper mesh, composite copper mesh and etched capillary structure.
  • foam copper copper, copper mesh, composite copper mesh and etched capillary structure.
  • the temperature-averaging board needs to develop in a thinner direction.
  • the size of other components is required to be smaller and thinner, which makes the thickness of the temperature spreader more stringent.
  • ultra-thin temperature spreaders with a thickness of less than 280 ⁇ m came into being.
  • Ultra-thin temperature spreaders need to have thinner liquid wicks while improving heat transfer performance.
  • the liquid wicks in existing temperature spreaders are relatively thick, and their water absorption and heat transfer performances are poor, which cannot meet the needs of electronic products to develop towards smaller sizes.
  • the purpose of the present invention is to provide a copper paste for printing a capillary structure to solve the problem that the thickness of the liquid absorbent core in the existing temperature equalizing plate is relatively thick, the water absorption performance and the heat transfer performance are both poor, and the demand for the development of electronic products to be smaller cannot be met.
  • the present invention provides a copper paste for printing a capillary structure, wherein the copper paste is composed of copper powder, a polymer, a solvent, a binder, a dispersant, a leveling agent, a bonding enhancer and an antioxidant, wherein the particle size of the copper powder ranges from 0.5 ⁇ m to 10 ⁇ m, and the particle size of the microspheres of the polymer is from 1 ⁇ m to 50 ⁇ m.
  • the particle size of the microspheres of the high molecular polymer is one or more of 300 mesh to 1000 mesh, 1000 mesh to 3000 mesh, and 5000 mesh to 12000 mesh, and the porosity of the high molecular polymer is 35% to 75%.
  • the high molecular polymer is one or more of polymethyl methacrylate, polyisobutyl methacrylate, methyl methacrylate-isobutyl methacrylate copolymer, polyoxymethylene, polyurethane and polystyrene.
  • the solvent is one or more of ethanol, propanol, isopropanol, n-butanol, ethylene glycol, 1,2-propylene glycol, 1,2-butanediol, 1,4-butanediol and water.
  • the binder is one or more of polyvinyl pyrrolidone (PVP), polyvinyl alcohol (PVA), polyvinyl butyral (PVB), polyurethane, hydroxymethyl cellulose and ethyl cellulose.
  • PVP polyvinyl pyrrolidone
  • PVA polyvinyl alcohol
  • PVB polyvinyl butyral
  • polyurethane polyurethane
  • the dispersant is one or more of methylpentanol, cellulose derivatives, polyacrylamide and fatty acid polyethylene glycol ester.
  • the leveling agent is one or more of sodium dodecyl sulfate, sodium dodecylbenzene sulfonate, sodium tetradecyl sulfonate, sodium hexadecyl sulfonate, lecithin, triethanolamine, KH550, polyethylene glycol, triethanolamine, Tween 80 and Span 80.
  • the tackifier is a high-viscosity resin
  • the high-viscosity gum is one or more of natural rubber, styrene-butadiene rubber, chloroprene rubber, C5 and C9 petroleum resins.
  • the antioxidant is one or more of citric acid, phytic acid, vitamins, oxalic acid, ascorbic acid and glucose.
  • the mass ratio of the copper powder to the polymer is 8-9:1, the mass fraction of the solvent is 1%-70% after the copper powder and the polymer are mixed, the mass fraction of the binder is 0.1%-30% after the copper powder and the polymer are mixed, the mass fraction of the dispersant is 0.01%-5% after the copper powder and the polymer are mixed, the mass fraction of the leveling agent is 0.01%-10% after the copper powder and the polymer are mixed, the mass fraction of the bonding enhancer is 0.01%-5% after the copper powder and the polymer are mixed, and the mass fraction of the antioxidant is 0.01%-10% after the copper powder and the polymer are mixed.
  • the average particle size of the copper powder is 3 ⁇ m.
  • the present invention provides a method for preparing the copper paste for printing a capillary structure as described above, comprising the following steps:
  • the high molecular polymer and the copper powder are firstly mixed uniformly;
  • the solvent, the binder, the dispersant, the leveling agent, the adhesion promoter and the antioxidant are added and fully stirred in a mixer for 0.5 h to 6 h.
  • the copper paste for printing capillary structure in the present invention adopts copper powder, high molecular polymer, solvent, binder, dispersant, leveling agent, adhesion promoter and antioxidant as raw material components, and limits the particle size range of copper powder and the particle size range of microspheres of high molecular polymer, so that the prepared copper paste can be coated on the carrier of the temperature equalizing plate by scraping or screen printing, and then used as a liquid wick after debinding and sintering with hydrogen or hydrogen-nitrogen mixed gas, so as to reduce the investment in equipment and reduce the cost.
  • the thickness of the liquid wick can be accurately controlled within 10 ⁇ m ⁇ 100 ⁇ m, the structural strength is higher, and the water absorption performance and heat transfer performance are better, which meets the demand for the development of electronic products towards smaller size.
  • FIG1 is a step diagram of a method for preparing a copper paste for printing a capillary structure according to an embodiment of the present invention
  • FIG2 is a schematic diagram of the surface state of a first liquid-absorbing core provided by an embodiment of the present invention.
  • FIG. 3 is a schematic diagram of the surface state of a second liquid-absorbing core provided by an embodiment of the present invention.
  • An embodiment of the present invention provides a copper paste for printing a capillary structure, wherein the copper paste is composed of copper powder, a high molecular polymer (pore former), a solvent, a binder, a dispersant, a leveling agent, a bonding agent and an antioxidant.
  • the copper paste is composed of copper powder, a high molecular polymer (pore former), a solvent, a binder, a dispersant, a leveling agent, a bonding agent and an antioxidant.
  • the mass ratio of the copper powder to the high molecular polymer is 8-9:1
  • the mass fraction of the solvent is 1%-70% after the copper powder and the high molecular polymer are mixed
  • the mass fraction of the binder is 0.1%-30% after the copper powder and the high molecular polymer are mixed
  • the mass fraction of the dispersant is 0.01%-5% after the copper powder and the high molecular polymer are mixed
  • the mass fraction of the leveling agent is 0.01%-10% after the copper powder and the high molecular polymer are mixed
  • the mass fraction of the bonding enhancer is 0.01%-5% after the copper powder and the high molecular polymer are mixed
  • the mass fraction of the antioxidant is 0.01%-10% after the copper powder and the high molecular polymer are mixed.
  • the particle size of the copper powder is in the range of 0.5 to 10 ⁇ m, and the average particle size (D50 or median particle size) is 3 ⁇ m; the particle size of the microspheres of the high molecular polymer is in the range of 1 ⁇ m to 50 ⁇ m.
  • the particle size of the microspheres of the polymer is one or more of 300-1000 mesh, 1000-3000 mesh and 5000-12000 mesh.
  • the particle size of the microspheres of the polymer is divided into ten categories, namely 300 mesh, 500 mesh, 800 mesh, 1000 mesh, 2000 mesh, 3000 mesh, 5000 mesh, 8000 mesh, 10000 mesh and 12000 mesh.
  • 300-1000 mesh is fine powder
  • 1000-3000 mesh is fine powder
  • 5000-12000 mesh is ultrafine powder.
  • the porosity of the polymer is 35%-75%.
  • the prepared copper paste can be applied to copper layers below 20 ⁇ m; if the particle size of the microsphere of the polymer selected is 1000-3000 mesh, the prepared copper paste can be applied to copper layers between 20 ⁇ m and 40 ⁇ m; if the particle size of the microsphere of the polymer selected is 300-1000 mesh, the prepared copper paste can be applied to copper layers between 30 ⁇ m and 60 ⁇ m.
  • the different particle sizes of the microsphere of the polymer can be used alone or in combination to change the surface or internal morphology of the porous copper layer.
  • the high molecular polymer is one or more of polymethyl methacrylate, polyisobutyl methacrylate, methyl methacrylate-isobutyl methacrylate copolymer, polyoxymethylene, polyurethane and polystyrene.
  • the solvent is one or more of ethanol, propanol, isopropanol, n-butanol, ethylene glycol, 1,2-propylene glycol, 1,2-butanediol, 1,4-butanediol and water.
  • the binder is one or more of polyvinyl pyrrolidone (PVP), polyvinyl alcohol (PVA), polyvinyl butyral (PVB), polyurethane, hydroxymethyl cellulose and ethyl cellulose.
  • PVP polyvinyl pyrrolidone
  • PVA polyvinyl alcohol
  • PVB polyvinyl butyral
  • polyurethane polyurethane
  • the dispersant is one or more of methyl amyl alcohol, cellulose derivatives, polyacrylamide and fatty acid polyethylene glycol ester.
  • the leveling agent is one or more of sodium dodecyl sulfate, sodium dodecylbenzene sulfonate, sodium tetradecyl sulfonate, sodium hexadecyl sulfonate, lecithin, triethanolamine, KH550, polyethylene glycol, triethanolamine, Tween 80 and Span 80.
  • the tackifier is a high-viscosity resin
  • the high-viscosity gum is one or more of natural rubber, styrene-butadiene rubber, chloroprene rubber, C5 and C9 petroleum resins.
  • the antioxidant is one or more of citric acid, phytic acid, vitamins, oxalic acid, ascorbic acid and glucose.
  • the mass fraction of the solvent is 5% to 40% after the copper powder and the polymer are mixed
  • the mass fraction of the binder is 0.1% to 15% after the copper powder and the polymer are mixed
  • the mass fraction of the dispersant is 0.01% to 2% after the copper powder and the polymer are mixed
  • the mass fraction of the leveling agent is 0.01% to 4% after the copper powder and the polymer are mixed
  • the mass fraction of the bonding enhancer is 0.01% to 2% after the copper powder and the polymer are mixed
  • the mass fraction of the antioxidant is 0.01% to 5% after the copper powder and the polymer are mixed.
  • the limitation of the copper powder can effectively ensure that the copper paste still has high structural strength at an ultra-thin thickness; the limitation of the high molecular polymer can enable the copper paste to form a uniform capillary structure after coating and sintering; the limitation of the binder and the thickener as the bonding phase of the system can enable the copper paste to maintain a certain viscosity and prevent the copper powder from settling; the limitation of the dispersant can ensure that the copper powder and the high molecular polymer of different sizes can be evenly distributed and not agglomerated; the limitation of the leveling agent can enable the copper paste to maintain a uniform thickness during coating; the limitation of the antioxidant can prevent the copper paste from deteriorating and failing due to oxidation reaction during storage.
  • the copper paste for printing capillary structure is referred to as copper paste.
  • the principle is to use the polymer with a microsphere particle size between 1 ⁇ m and 50 ⁇ m, and a solvent that does not dissolve or swell with the polymer. After coating, the polymer is evenly dispersed around the copper powder, occupying the space, and a porous copper layer structure is formed after debinding. The copper particles are then sintered to adhere and collapse under the action of gravity to form a porous copper layer structure with a certain structural strength.
  • the general idea of preparing copper paste for capillary printing is that the porosity of copper oxide is basically about 50% due to the theoretical shrinkage volume after the reduction of copper oxide, while the porosity of the copper paste described in the design idea of this embodiment can reach 60% ⁇ 70%.
  • the high molecular polymer in different microsphere particle size ranges can form different pore morphologies, that is, fewer closed pores and more open pores, and they are distributed in a three-dimensional continuous manner. Therefore, when applied to the water absorption layer of the liquid absorbent core, the characteristics of high porosity and multiple open pores can effectively and quickly exert the capillary force.
  • the method for preparing the copper paste for printing the capillary structure comprises the following steps:
  • the coating method of the copper paste composed of the above raw material components is as follows: the copper paste is first coated on a carrier of a temperature-averaging plate by scraping or screen printing; the coated sample is then carried on ceramic or quartz glass, and debinding is performed at 400°C to 600°C in a nitrogen atmosphere; finally, the sample after debinding is subjected to high-temperature sintering treatment in a sintering furnace in an atmosphere of hydrogen or a hydrogen-nitrogen mixture, and the porous copper layer finally obtained is used as the liquid wick of the temperature-averaging plate.
  • the coating step can be performed once or multiple times to control the thickness according to the required thickness, that is, the structure and size design of different liquid wicks of the temperature homogenizing plate can be flexibly realized.
  • the debinding step a large amount of exhaust gas will be generated during the debinding process, so the equipment needs to be equipped with an exhaust gas absorption device. In order to ensure the flow of gas during the debinding process, a large flow of nitrogen is required.
  • This step can be carried out in a debinding furnace or directly in a sintering furnace to reduce the cost of using the equipment.
  • the thermal decomposition of other components except the copper powder needs to be controlled to occur in the same temperature range.
  • the sintering temperature is 700°C to 900°C, preferably 800°C to 850°C, and the time is 0.5h to 24h, preferably 2h to 12h.
  • the sintering temperature can be set to less than 850°C and the sintering time can be set to less than 2h.
  • the copper paste for printing the capillary structure in the present embodiment adopts copper powder, high molecular polymer, solvent, binder, dispersant, leveling agent, adhesion promoter and antioxidant as raw material components, and limits the particle size range of copper powder and the particle size range of microspheres of high molecular polymer, so that the prepared copper paste can be coated on the carrier of the temperature uniform plate by scraping or screen printing, and then used as a liquid wick after debinding and sintering with hydrogen or hydrogen-nitrogen mixed gas.
  • the thickness of the liquid wick can be accurately controlled at 10 ⁇ m ⁇ 100 ⁇ m to meet the demand for the development of smaller electronic products, and its viscosity is 10000cps ⁇ 35000cps.
  • the copper paste for printing capillary structures can adjust the parameters such as the porosity and pore morphology of the product at any time according to actual needs, and its performance indicators such as sintering thickness, water absorption rate, structural strength, etc. are better than those of copper mesh, composite copper mesh and copper oxide printing copper paste; when the copper paste for printing capillary structures is coated, fully automatic scraping or screen printing equipment can be used, and the preparation of porous copper layers can be completed at high throughput in combination with a tunnel furnace, and when performing the process steps of debinding and sintering, it can be completed in a sintering furnace at one time, reducing the investment in equipment; after being stored for a long time, the copper paste for printing capillary structures only needs simple stirring to be used, which improves the convenience of use; the copper paste for printing capillary structures also has a three-dimensional mutually interpenetrating open space structure with a pore size of 1 ⁇ m ⁇ 30 ⁇ m and a porosity of about 50% ⁇ 70%; the copper
  • Electrolytic copper powder with an average particle size of 10 ⁇ m and polymethyl methacrylate microspheres (PMMA microspheres) with a particle size of 3000 mesh are mixed together in a mass ratio of 8:1, and the mixed powder is added to a polyvinyl butyral PVB-ethylene glycol solution with a mass fraction of 10% of the mixed powder.
  • a viscosity enhancer with a mass fraction of 0.5% of the mixed powder, a dispersant with a mass fraction of 0.5% of the mixed powder, an antioxidant with a mass fraction of 1% of the mixed powder, and other components in the above copper slurry are added in sequence, and stirring is continued for 0.5h to 6h.
  • the mixed copper slurry is then scraped onto the VC sample (the carrier of the temperature equalizer), and then baked in an oven at 90°C ⁇ 100°C for 20 min. After the solvent is dried, it is placed in a sintering furnace, and N2 (nitrogen) is first introduced and the binder is debonded at 450°C for 90 minutes. Finally, N2/H2 (hydrogen) is introduced and sintered at 700°C ⁇ 800°C for 120 min, finally obtaining a VC sample with a porous capillary structure.
  • Electrolytic copper powder with an average particle size of 5 ⁇ m and polyisobutyl methacrylate microspheres (PiBMA microspheres) with a particle size of 3000 mesh are mixed together in a mass ratio of 9:1, and the mixed powder is added to a polyvinyl pyrrolidone PVP-1,2-propylene glycol solution with a mass fraction of 8% of the mixed powder.
  • a viscosity enhancer with a mass fraction of 0.5% of the mixed powder, a dispersant with a mass fraction of 0.5% of the mixed powder, an antioxidant with a mass fraction of 1% of the mixed powder, and other components in the above copper slurry are added in sequence, and stirring is continued for 0.5h to 6h.
  • the mixed copper slurry is then scraped onto the VC sample, and then baked in an oven at 90°C ⁇ 100°C for 30 min. After the solvent is dried, it is placed in a sintering furnace, first N2 is introduced and the binder is debonded at 450°C for 120 min, and finally N2/H2 is introduced and sintered at 800°C ⁇ 850°C for 120 min, finally obtaining a VC sample with a porous capillary structure.
  • Polymethyl methacrylate microspheres with a particle size of 500 mesh and polyoxymethylene microspheres (POM microspheres) with a particle size of 3000 mesh are mixed in a mass ratio of 3:1 to form a composite powder.
  • Electrolytic copper powder with an average particle size of 5 ⁇ m is mixed with the composite powder in a mass ratio of 8:1.
  • the mixed powder is added to a vinyl cellulose-1,2-propylene glycol solution with a mass fraction of 10% of the mixed powder, and after being fully stirred in a mixer, a viscosity enhancer with a mass fraction of 0.5% of the mixed powder, a dispersant with a mass fraction of 0.5% of the mixed powder, an antioxidant with a mass fraction of 1% of the mixed powder, and other components in the above copper slurry are added in sequence, and stirring is continued for 0.5h to 6h.
  • the mixed copper slurry is then scraped onto the VC sample, and then baked in an oven at 90°C ⁇ 100°C for 20 min. After the solvent is dried, it is placed in a sintering furnace. N2 is first introduced and the binder is debonded at 500°C for 90 min. Finally, N2/H2 is introduced and sintered at 700°C ⁇ 800°C for 120 min, finally obtaining a VC sample with a porous capillary structure.
  • Polymethyl methacrylate microspheres with particle sizes of 500 mesh and 3000 mesh are mixed in a mass ratio of 4:1 to form a composite powder.
  • Electrolytic copper powder with an average particle size of 3 ⁇ m is mixed with the composite powder in a mass ratio of 8:1.
  • the mixed powder is added to a mixed solution of vinyl cellulose-1,2-propylene glycol and ethylene glycol (volume ratio of 4:1) with a mass fraction of 10% of the mixed powder, and after being fully stirred in a mixer, a viscosity enhancer with a mass fraction of 0.5% of the mixed powder, a dispersant with a mass fraction of 0.5% of the mixed powder, an antioxidant with a mass fraction of 1% of the mixed powder, and other components in the above copper slurry are added in sequence, and stirring is continued for 0.5h to 6h.
  • the mixed copper slurry is then scraped onto the VC sample, and then baked in an oven at 90°C ⁇ 100°C for 30 min. After the solvent is dried, it is placed in a sintering furnace. N2 is first introduced and the binder is debonded at 450°C for 90 min. Finally, N2/H2 is introduced and sintered at 700°C ⁇ 800°C for 120 min, finally obtaining a VC sample with a porous capillary structure.
  • Electrolytic copper powder with an average particle size of 10 ⁇ m and polymethyl methacrylate microspheres with a particle size of 1000 mesh are mixed together in a mass ratio of 8:1, and the mixed powder is added to a polyvinyl pyrrolidone PVP-1,2-propylene glycol solution with a mass fraction of 15% of the mixed powder.
  • a viscosity enhancer with a mass fraction of 0.5% of the mixed powder, a dispersant with a mass fraction of 0.5% of the mixed powder, an antioxidant with a mass fraction of 1% of the mixed powder, and other components in the above copper slurry are added in sequence, and stirring is continued for 0.5h to 6h.
  • the mixed copper slurry is then scraped onto the VC sample, and then baked in an oven at 90°C ⁇ 100°C for 20 min. After the solvent is dried, it is placed in a sintering furnace, and N2 (nitrogen) is first introduced and the binder is debonded at 450°C for 90 min. Finally, N2/H2 is introduced and sintered at 700°C ⁇ 800°C for 120 min, finally obtaining a VC sample with a porous capillary structure.
  • Electrolytic copper powder with an average particle size of 10 ⁇ m and polyisobutyl methacrylate microspheres with a particle size of 1000 mesh were mixed in a mass ratio of 8:1, and the mixed powder was added to a polyvinyl pyrrolidone PVP-1,2-propylene glycol solution with a mass fraction of 15% of the mixed powder.
  • a viscosity enhancer with a mass fraction of 0.5% of the mixed powder, a dispersant with a mass fraction of 0.5% of the mixed powder, an antioxidant with a mass fraction of 1% of the mixed powder, and other components in the above copper slurry were added in sequence, and stirring was continued for 0.5h to 6h.
  • the mixed copper slurry is then scraped onto the VC sample, and then baked in an oven at 90°C ⁇ 100°C for 20 min. After the solvent is dried, it is placed in a sintering furnace, and N2 (nitrogen) is first introduced and the binder is debonded at 450°C for 90 min. Finally, N2/H2 is introduced and sintered at 700°C ⁇ 800°C for 120 min, finally obtaining a VC sample with a porous capillary structure.
  • Electrolytic copper powder with an average particle size of 10 ⁇ m and polyoxymethylene microspheres (POM microspheres) with a particle size of 1000 mesh are mixed together in a mass ratio of 7:1, and the mixed powder is added to a mixed solution of polyvinyl butyral PVB-ethylene glycol and isobutyl alcohol (volume ratio of 5:1) with a mass fraction of 15% of the mixed powder, and after fully stirring in a mixer, a viscosity enhancer with a mass fraction of 0.5% of the mixed powder, a dispersant with a mass fraction of 0.5% of the mixed powder, an antioxidant with a mass fraction of 1% of the mixed powder, and other components in the above copper slurry are added in sequence, and stirring is continued for 0.5h ⁇ 6h.
  • POM microspheres polyoxymethylene microspheres
  • the mixed copper slurry is then scraped onto the VC sample, and then baked in an oven at 90°C ⁇ 100°C for 20 min. After the solvent is dried, it is placed in a sintering furnace, and N2 (nitrogen) is first introduced and the binder is debonded at 500°C for 90 min. Finally, N2/H2 is introduced and sintered at 800°C ⁇ 850°C for 120 min, finally obtaining a VC sample with a porous capillary structure.
  • N2 nitrogen
  • Polymethyl methacrylate microspheres with particle sizes of 500 mesh, 2000 mesh and 8000 mesh are mixed in a mass ratio of 4:1:1 to form a composite powder.
  • Electrolytic copper powder with an average particle size of 3 ⁇ m is mixed with the composite powder in a mass ratio of 7:1.
  • the mixed powder is added to a mixed solution of vinyl cellulose-1,2-butanediol and ethylene glycol (volume ratio of 4:1) with a mass fraction of 6% of the mixed powder, and after being fully stirred in a mixer, a viscosity enhancer with a mass fraction of 0.5% of the mixed powder, a dispersant with a mass fraction of 0.5% of the mixed powder, an antioxidant with a mass fraction of 1% of the mixed powder, and other components in the above copper slurry are added in sequence, and stirring is continued for 0.5h to 6h.
  • the mixed copper slurry is then scraped onto the VC sample, and then baked in an oven at 90°C ⁇ 110°C for 30 min. After the solvent is dried, it is placed in a sintering furnace. N2 is first introduced and the binder is debonded at 450°C for 90 min. Finally, N2/H2 is introduced and sintered at 700°C ⁇ 800°C for 120 min, finally obtaining a VC sample with a porous capillary structure.
  • Polymethyl methacrylate microspheres with particle sizes of 300 mesh, 2000 mesh and 8000 mesh are mixed in a mass ratio of 4:1:1 to form a composite powder.
  • Electrolytic copper powder with an average particle size of 3 ⁇ m is mixed with the composite powder in a mass ratio of 7:1.
  • the mixed powder is added to a mixed solution of vinyl cellulose-1,2-butanediol and 1,2-propylene glycol (volume ratio of 1:1) with a mass fraction of 10% of the mixed powder, and after fully stirring in a mixer, a viscosity enhancer with a mass fraction of 0.5% of the mixed powder, a dispersant with a mass fraction of 0.5% of the mixed powder, an antioxidant with a mass fraction of 1% of the mixed powder, and other components in the above copper slurry are added in sequence, and stirring is continued for 0.5h to 6h.
  • the mixed copper slurry is then scraped onto the VC sample, and then baked in an oven at 90°C ⁇ 110°C for 30 min. After the solvent is dried, it is placed in a sintering furnace. N2 is first introduced and the binder is debonded at 450°C for 90 min. Finally, N2/H2 is introduced and sintered at 700°C ⁇ 800°C for 120 min, finally obtaining a VC sample with a porous capillary structure.
  • Polymethyl methacrylate microspheres with particle sizes of 300 mesh, 3000 mesh and 12000 mesh are mixed in a mass ratio of 4:2:1 to form a composite powder, and electrolytic copper powder with an average particle size of 3 ⁇ m is mixed with the composite powder in a mass ratio of 8:1.
  • the mixed powder is added to a mixed solution of polyvinyl alcohol-1,2-butanediol and isobutyl alcohol (volume ratio 5:1) with a mass fraction of 8% of the mixed powder, and after being fully stirred in a mixer, a viscosity enhancer with a mass fraction of 0.5% of the mixed powder, a dispersant with a mass fraction of 0.5% of the mixed powder, an antioxidant with a mass fraction of 1% of the mixed powder, and other components in the above copper slurry are added in sequence, and stirring is continued for 0.5h to 6h.
  • the mixed copper slurry is then scraped onto the VC sample, and then baked in an oven at 90°C ⁇ 110°C for 30 min. After the solvent is dried, it is placed in a sintering furnace. N2 is first introduced and the binder is debonded at 450°C for 90 min. Finally, N2/H2 is introduced and sintered at 700°C ⁇ 800°C for 120 min, finally obtaining a VC sample with a porous capillary structure.

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Abstract

一种用于印刷毛细结构的铜浆及其制备方法，所述铜浆由铜粉、高分子聚合物、溶剂、粘结剂、分散剂、流平剂、增粘结以及抗氧化剂组成，所述铜粉的粒径范围为0.5μm～10μm，所述高分子聚合物的微球粒径为1μm～50μm；铜浆通过对铜粉和高分子聚合物进行限定，从而可以使制备得到的铜浆经刮涂或丝网印刷涂布于均温板的承载物，再经排胶以及氢气或氢氮混合气烧结后作为吸液芯，以减少设备的投入，降低成本，且该吸液芯的厚度可以精准控制在10μm～100μm，结构强度更高，吸水性能和传热性能均更好，满足了电子产品往更小型化发展的需求。

Description

用于印刷毛细结构的铜浆及其制备方法 技术领域
本发明涉及均温板技术领域，尤其涉及一种用于印刷毛细结构的铜浆及其制备方法。
 背景技术
电子元器件及集成电路技术的高频、高速发展，会导致电子元件在运行过程中产生大量的热量，如计算机CPU运行过程中的热流密度已经达到60-100 W/cm2，半导体激光器中甚至高达103 W/cm2。
电子设备工作的可靠性对温度极其敏感，其元器件温度在70~80℃的水平上每增加1℃，可靠性就会下降5%，所以高热流对元器件正常工作的可靠性造成了极大的威胁，因此散热成了电子产品小型化发展的关键问题。为了保证电子元器件的正常运行，通常在电子元器件上加装散热器为其散热，现在的主流设计为在散热器和电子元器件之间加装具有良好热传导性的均温板，该均温板的作用是将发热电子元器件的热量先均匀分布，然后在通过散热器散发出去。
均温板是依靠自身内部工作流体相变实现快速传热的导热组件，主要包括上下盖板或金属管、密封头、吸液芯和传热工质。其中，吸液芯的毛细结构直接影响到均温板的性能，毛细结构需要毛细力强且水流阻力小。
均温板中具有毛细结构的吸液芯的种类繁多，如泡沫铜、铜网、复合铜网以及蚀刻毛细结构，而因结构及空间等限制因数，均温板需要向更薄的方向进行发展。
由于电子产品往小型化的不断发展，需要求其它组成的元器件的尺寸越来越小且越来越薄，这就使得均温板在厚度上提出更加苛刻的要求，如280 μm以下厚度的超薄均温板应运而生，超薄的均温板在提升传热性能的同时还需要有更薄的吸液芯，但现有均温板中吸液芯的厚度较厚，吸水性能和传热性能均较差，无法满足电子产品往更小型化发展的需求。
因此，有必要提供一种用于印刷毛细结构的铜浆来解决上述技术问题。
 技术问题
本发明的目的在于提供一种用于印刷毛细结构的铜浆，以解决现有均温板中吸液芯的厚度较厚，吸水性能和传热性能均较差，无法满足电子产品往更小型化发展的需求的问题。
 技术解决方案
第一方面，本发明提供了一种用于印刷毛细结构的铜浆，所述铜浆由铜粉、高分子聚合物、溶剂、粘结剂、分散剂、流平剂、增粘结以及抗氧化剂组成，所述铜粉的粒径范围为0.5μm ~10μm，所述高分子聚合物的微球粒径为1μm ~50μm。
优选的，所述高分子聚合物的微球粒径为300目~1000目、1000目~3000目以及5000目~12000目中的一种或多种，所述高分子聚合物的孔隙率为35%~75%。
优选的，所述高分子聚合物为聚甲基丙烯酸甲酯、聚甲基丙烯酸异丁酯、甲基丙烯酸甲酯-甲基丙烯酸异丁酯共聚物、聚甲醛、聚氨酯以及聚苯乙烯中的一种或多种。
优选的，所述溶剂为乙醇、丙醇、异丙醇、正丁醇、乙二醇、1,2-丙二醇、1,2-丁二醇、1,4-丁二醇以及水中的一种或多种
优选的，所述粘结剂为聚乙烯吡咯烷酮PVP、聚乙烯醇PVA、聚乙烯缩丁醛PVB、聚氨酯、羟甲基纤维素以及乙基纤维素中的一种或多种。
优选的，所述分散剂为甲基戊醇、纤维素衍生物、聚丙烯酰胺以及脂肪酸聚乙二醇酯中的一种或多种。
优选的，所述流平剂为十二烷基硫酸钠、十二烷基苯磺酸钠、十四烷基磺酸钠、十六烷基磺酸钠、卵磷脂、三乙醇胺、KH550、聚乙二醇、三乙醇胺、吐温80以及司盘80中的一种或多种。
优选的，所述增粘剂为高粘度树脂，所述高粘度树胶为天然橡胶、丁苯橡胶、氯丁橡胶、C5以及C9类石油树脂中的一种或多种。
优选的，所述抗氧化剂为柠檬酸、植酸、维生素、草酸、抗坏血酸以及葡萄糖中的一种或多种。
优选的，所述铜粉与所述高分子聚合物的质量比为8~9:1，所述溶剂的质量分数为所述铜粉与所述高分子聚合物混合后的1%~70%，所述粘结剂的质量分数为所述铜粉与所述高分子聚合物混合后的0.1%~30%，所述分散剂的质量分数为所述铜粉与所述高分子聚合物混合后的0.01%~5%，所述流平剂的质量分数为所述铜粉与所述高分子聚合物混合后的0.01%~10%，所述增粘结的质量分数为所述铜粉与所述高分子聚合物混合后的0.01%~5%，所述抗氧化剂的质量分数为所述铜粉与所述高分子聚合物混合后的0.01%~10%。
优选的，所述铜粉的平均粒径为3μm。
第二方面，本发明提供了一种如上所述的用于印刷毛细结构的铜浆的制备方法，其包括以下步骤：
按所述铜浆的组分，先将所述高分子聚合物与所述铜粉混合均匀；
之后再加入所述溶剂、所述粘结剂、所述分散剂、所述流平剂、所述增粘结以及所述抗氧化剂，并在混料机中充分搅拌0.5h~6h。
 有益效果
与相关技术相比，本发明中用于印刷毛细结构的铜浆通过采用铜粉、高分子聚合物、溶剂、粘结剂、分散剂、流平剂、增粘结以及抗氧化剂作为原料组分，并限定铜粉的粒径范围以及高分子聚合物的微球粒径范围，从而可以使制备得到的铜浆经刮涂或丝网印刷涂布于均温板的承载物，再经排胶以及氢气或氢氮混合气烧结后作为吸液芯，以减少设备的投入，降低成本，且该吸液芯的厚度可以精准控制在10μm~100μm，结构强度更高，吸水性能和传热性能均更好，满足了电子产品往更小型化发展的需求。
 附图说明
为了更清楚地说明本发明实施例中的技术方案，下面将对实施例描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本发明的一些实施例，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其它的附图，其中：
图1为本发明实施例提供一种用于印刷毛细结构的铜浆的制备方法的步骤图；
图2为本发明实施例提供的第一种吸液芯的表面状态示意图；
图3为本发明实施例提供的第二种吸液芯的表面状态示意图。
 本发明的实施方式
下面将对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅是本发明的一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其它实施例，都属于本发明保护的范围。
本发明实施例提供了一种用于印刷毛细结构的铜浆，所述铜浆由铜粉、高分子聚合物（造孔剂）、溶剂、粘结剂、分散剂、流平剂、增粘结以及抗氧化剂组成。
其中，所述铜粉与所述高分子聚合物的质量比为8~9:1，所述溶剂的质量分数为所述铜粉与所述高分子聚合物混合后的1%~70%，所述粘结剂的质量分数为所述铜粉与所述高分子聚合物混合后的0.1%~30%，所述分散剂的质量分数为所述铜粉与所述高分子聚合物混合后的0.01%~5%，所述流平剂的质量分数为所述铜粉与所述高分子聚合物混合后的0.01%~10%，所述增粘结的质量分数为所述铜粉与所述高分子聚合物混合后的0.01%~5%，所述抗氧化剂的质量分数为所述铜粉与所述高分子聚合物混合后的0.01%~10%。
所述铜粉的粒径范围为0.5~10μm，平均粒径（D50或中粒径）为3μm；所述高分子聚合物的微球粒径为1μm ~50μm。
所述高分子聚合物的微球粒径为300目~1000目、1000目~3000目以及5000目~12000目中的一种或多种，所述高分子聚合物的微球粒径分为十类，分别为300目、500目、800目、1000目、2000目、3000目、5000目、8000目、10000目以及12000目，300目~1000目为细粉类，1000目~3000目为细微粉类，5000~12000目为超细粉类；所述高分子聚合物的孔隙率为35%~75%。
若选用的所述高分子聚合物的微球粒径为5000目~12000目，则可以使制备得到的铜浆适用于20μm以下铜层的应用；若选用的所述高分子聚合物的微球粒径为1000目~3000目，则可以使制备得到的铜浆适用于20μm~40μm之间铜层的应用；若选用的所述高分子聚合物的微球粒径为300目~1000目，则可以使制备得到的铜浆适用于30μm~60μm之间铜层的应用。所述高分子聚合物的不同微球粒径可以单独使用，也可以混合使用，以改变多孔铜层的表面或者内部的形貌。
所述高分子聚合物为聚甲基丙烯酸甲酯、聚甲基丙烯酸异丁酯、甲基丙烯酸甲酯-甲基丙烯酸异丁酯共聚物、聚甲醛、聚氨酯以及聚苯乙烯中的一种或多种。
所述溶剂为乙醇、丙醇、异丙醇、正丁醇、乙二醇、1,2-丙二醇、1,2-丁二醇、1,4-丁二醇以及水中的一种或多种。
所述粘结剂为聚乙烯吡咯烷酮PVP、聚乙烯醇PVA、聚乙烯缩丁醛PVB、聚氨酯、羟甲基纤维素以及乙基纤维素中的一种或多种。
所述分散剂为甲基戊醇、纤维素衍生物、聚丙烯酰胺以及脂肪酸聚乙二醇酯中的一种或多种。
所述流平剂为十二烷基硫酸钠、十二烷基苯磺酸钠、十四烷基磺酸钠、十六烷基磺酸钠、卵磷脂、三乙醇胺、KH550、聚乙二醇、三乙醇胺、吐温80以及司盘80中的一种或多种。
所述增粘剂为高粘度树脂，所述高粘度树胶为天然橡胶、丁苯橡胶、氯丁橡胶、C5以及C9类石油树脂中的一种或多种。
所述抗氧化剂为柠檬酸、植酸、维生素、草酸、抗坏血酸以及葡萄糖中的一种或多种。
优选的，所述溶剂的质量分数为所述铜粉与所述高分子聚合物混合后的5%~40%，所述粘结剂的质量分数为所述铜粉与所述高分子聚合物混合后的0.1%~15%，所述分散剂的质量分数为所述铜粉与所述高分子聚合物混合后的0.01%~2%，所述流平剂的质量分数为所述铜粉与所述高分子聚合物混合后的0.01%~4%，所述增粘结的质量分数为所述铜粉与所述高分子聚合物混合后的0.01%~2%，所述抗氧化剂的质量分数为所述铜粉与所述高分子聚合物混合后的0.01%~5%。
所述铜粉的限定能有效地保证所述铜浆在超薄的厚度下仍然有很高的结构强度；所述高分子聚合物的限定可以使所述铜浆在涂布烧结后形成均匀的毛细结构；所述粘结剂和所述增粘剂的限定作为体系的粘结相，可以使所述铜浆保持一定的粘度，防止所述铜粉沉降；所述分散剂的限定可以保证大小的所述铜粉、所述高分子聚合物能均匀分数，不团结成块；所述流平剂的限定则可以使所述铜浆在涂布时保持均匀的厚度；所述抗氧化剂的限定可以防止所述铜浆在保存过程中因氧化反应而导致材料的变质失效。
所述用于印刷毛细结构的铜浆简称铜浆，原理为采用微球粒径在1μm ~50μm之间的所述高分子聚合物，以及与所述高分子聚合物不产生溶解以及溶胀等反应的溶剂，经涂布后所述高分子聚合物均匀的分散在所述铜粉周围，占据了空间，经排胶后形成多孔的铜层结构，再经烧结铜颗粒发生黏连，在重力作用下发生坍塌，形成具有一定结构强度的多孔铜层结构。
一般毛细印刷铜浆的制备思路-即铜的氧化物在因铜氧化物还原后的理论收缩体积限制其孔隙率基本在50%左右，而本实施例的设计思路中所述铜浆孔隙率可达到60%~70%，另一个显著特点为不同微球粒径区间的高分子聚合物，可形成不同的孔形貌，即闭孔少，开孔多，且呈三维连续的分布，因此在应用于吸液芯的吸水层时，高孔隙率、多开孔的特点，能有效、快速的发挥毛细力作用。
如图1所示，所述用于印刷毛细结构的铜浆的制备方法包括以下步骤：
S101、按所述铜浆的组分，先将所述高分子聚合物与所述铜粉混合均匀。
S102、之后再加入所述溶剂、所述粘结剂、所述分散剂、所述流平剂、所述增粘结以及所述抗氧化剂，并在混料机中充分搅拌0.5h~6h。
上述原料组分组成的铜浆的涂布方法为：所述铜浆先经刮涂或丝网印刷涂布于均温板的承载物；再将涂布完成的样品承载在陶瓷或石英玻璃上，并在氮气氛围下于400℃~600℃之间进行排胶；最后将排胶完成后的样品在氢气或氢氮混合气的氛围下的烧结炉子中进行高温烧结处理，最终得到的多孔铜层作为均温板的吸液芯。
其中，涂布的步骤可根据所需厚度采用一次涂布或多次涂布的方式进行厚度控制，即灵活的实现均温板不同吸液芯的结构及尺寸设计。
排胶的步骤中，因排胶过程会产生大量的废气，因此设备需要带有尾气吸收的装置，而为了保证排胶过程中气体的流动，则需采用大流量氮气，该步骤可以在排胶炉中进行，也可以直接在烧结炉中进行，减少设备的使用成本；为了保证所述多孔铜层的均一性，除了所述铜粉的其它组分的热分解均需要控制发生在同一温度段。
烧结的步骤中，烧结的温度为700℃~900℃，优选的为800℃~850℃，时间为0.5h~24h，优选的为2h~12h，为控制所述多孔铜层的孔隙率及结构两者之间的平衡，可将烧结温度设定为小于850℃，烧结时间设定为小于2h。
与相关技术相比，本实施例中用于印刷毛细结构的铜浆通过采用铜粉、高分子聚合物、溶剂、粘结剂、分散剂、流平剂、增粘结以及抗氧化剂作为原料组分，并限定铜粉的粒径范围以及高分子聚合物的微球粒径范围，从而可以使制备得到的铜浆经刮涂或丝网印刷涂布于均温板的承载物，再经排胶以及氢气或氢氮混合气烧结后作为吸液芯，该吸液芯的厚度可以精准控制在10μm~100μm，以满足电子产品往更小型化发展的需求，且其粘度为10000cps ~35000cps。
另外，该用于印刷毛细结构的铜浆可根据实际需求，随时调节产品的孔隙率以及孔道形貌等参数指标，且其烧结厚度、吸水速率、结构强度等性能指标优于铜网、复合铜网以及铜氧化物类的印刷铜浆；该用于印刷毛细结构的铜浆进行涂布时，可采用全自动刮涂或丝网印刷设备，以及搭配隧道炉可高通量完成多孔铜层的制备，且在执行排胶以及烧结的工序步骤时，在烧结炉中便可一次性完成，减少了设备的投入；该用于印刷毛细结构的铜浆在长时间保存后，只需要简单的搅拌即可使用，提升了使用的便捷性；该用于印刷毛细结构的铜浆还具有孔径在1μm ~30μm、孔隙率约为50%~70%的三维互相贯通的开孔空间结构；该用于印刷毛细结构的铜浆在不同微球粒径的所述高分子聚合物的情况下，可形成孔道不一的通道，减少单一小孔道在烧结过程中，因铜粉的塌陷而闭合。
结合图2和图3所示，采用所述高分子聚合物作为所述铜浆的组分时，将所述铜浆涂布于均温板的承载物上形成吸液芯后，该吸液芯的表面存在大小不同的坑洞，其坑洞的大小、密集程度可根据所述高分子聚合物的微球粒径大小以及使用量进行调节，且小颗粒的所述铜粉优先团聚在一起，而不是优先与大颗粒融合，最后导致其比表面积巨大，因此其毛细管直径更小，使其具有优异的毛细力，吸水速率极快。
为了能更好的理解本发明中用于印刷毛细结构的铜浆涂布于均温板的承载物的具体步骤，以下将通过更为具体的十个实施例进行解释；以下所述的各种组分均与上述各种组分的限定及范围相对应。
实施例一
取平均粒径为10μm的电解铜粉和粒径为3000目的聚甲基丙烯酸甲酯微球（PMMA微球）按8:1的质量比混合在一起，将该混合粉料加入质量分数为混合粉料的10%的聚乙烯醇缩丁醛PVB-乙二醇溶液中，并在混料机中充分搅拌后，依次加入质量分数为混合粉料的0.5%的增粘剂、质量分数为混合粉料的0.5%的分散剂、质量分数为混合粉料的1%的抗氧化剂以及上述铜浆中的其它组分，并继续搅拌0.5h ~6 h。
然后将混合好的铜浆刮涂到VC样品（均温板的承载物）上，之后放入90℃~100℃的烘箱中烘烤20 min，将其溶剂烘干后，放入烧结炉里，先通入N2（氮气）并于450℃的条件下排胶90min，最后通入N2/H2（氢气），并在700 ℃~800 ℃的条件下烧结120 min，最终得到具有多孔毛细结构的VC样品。
实施例二
取平均粒径为5μm的电解铜粉和粒径为3000目的聚甲基丙烯酸异丁酯微球（PiBMA微球）按9:1的质量比混合在一起，将该混合粉料加入质量分数为混合粉料的8%的聚乙烯吡咯烷酮PVP-1,2丙二醇溶液中，并在混料机中充分搅拌后，依次加入质量分数为混合粉料的0.5%的增粘剂、质量分数为混合粉料的0.5%的分散剂、质量分数为混合粉料的1%的抗氧化剂以及上述铜浆中的其它组分，并继续搅拌0.5h ~6 h。
然后将混合好的铜浆刮涂到VC样品上，之后放入90℃~100℃的烘箱中烘烤30 min，将其溶剂烘干后，放入烧结炉里，先通入N2并于450℃的条件下排胶120min，最后通入N2/H2，并在800 ℃~850 ℃的条件下烧结120 min，最终得到具有多孔毛细结构的VC样品。
实施例三
将粒径为500目的聚甲基丙烯酸甲酯微球与粒径为3000目的聚甲醛微球（POM微球）按3:1的质量比混合组成复合粉料，取平均粒径为5μm的电解铜粉与复合粉料按8:1的质量比混合在一起，将该混合粉料加入质量分数为混合粉料的10%的乙烯基纤维素-1,2丙二醇溶液中，并在混料机中充分搅拌后，依次加入质量分数为混合粉料的0.5%的增粘剂、质量分数为混合粉料的0.5%的分散剂、质量分数为混合粉料的1%的抗氧化剂以及上述铜浆中的其它组分，并继续搅拌0.5h ~6 h。
然后将混合好的铜浆刮涂到VC样品上，之后放入90℃~100℃的烘箱中烘烤20 min，将其溶剂烘干后，放入烧结炉里，先通入N2并于500℃的条件下排胶90min，最后通入N2/H2，并在700 ℃~800 ℃的条件下烧结120 min，最终得到具有多孔毛细结构的VC样品。
实施例四
将粒径为500目和3000目的聚甲基丙烯酸甲酯微球按4:1的质量比混合组成复合粉料，取平均粒径为3μm的电解铜粉与复合粉料按8:1的质量比混合在一起，将该混合粉料加入质量分数为混合粉料的10%的乙烯基纤维素-1,2丙二醇和乙二醇（体积比为4;1）的混合溶液中，并在混料机中充分搅拌后，依次加入质量分数为混合粉料的0.5%的增粘剂、质量分数为混合粉料的0.5%的分散剂、质量分数为混合粉料的1%的抗氧化剂以及上述铜浆中的其它组分，并继续搅拌0.5h ~6 h。
然后将混合好的铜浆刮涂到VC样品上，之后放入90℃~100℃的烘箱中烘烤30 min，将其溶剂烘干后，放入烧结炉里，先通入N2并于450℃的条件下排胶90min，最后通入N2/H2，并在700 ℃~800 ℃的条件下烧结120 min，最终得到具有多孔毛细结构的VC样品。
实施例五
取平均粒径为10μm的电解铜粉和粒径为1000目的聚甲基丙烯酸甲酯微球按8:1的质量比混合在一起，将该混合粉料加入质量分数为混合粉料的15%的聚乙烯吡咯烷酮PVP-1,2丙二醇溶液中，并在混料机中充分搅拌后，依次加入质量分数为混合粉料的0.5%的增粘剂、质量分数为混合粉料的0.5%的分散剂、质量分数为混合粉料的1%的抗氧化剂以及上述铜浆中的其它组分，并继续搅拌0.5h ~6 h。
然后将混合好的铜浆刮涂到VC样品上，之后放入90℃~100℃的烘箱中烘烤20 min，将其溶剂烘干后，放入烧结炉里，先通入N2（氮气）并于450℃的条件下排胶90min，最后通入N2/H2，并在700 ℃~800 ℃的条件下烧结120 min，最终得到具有多孔毛细结构的VC样品。
实施例六
取平均粒径为10μm的电解铜粉和粒径为1000目的聚甲基丙烯酸异丁酯微球按8:1的质量比混合在一起，将该混合粉料加入质量分数为混合粉料的15%的聚乙烯吡咯烷酮PVP-1,2丙二醇溶液中，并在混料机中充分搅拌后，依次加入质量分数为混合粉料的0.5%的增粘剂、质量分数为混合粉料的0.5%的分散剂、质量分数为混合粉料的1%的抗氧化剂以及上述铜浆中的其它组分，并继续搅拌0.5h ~6 h。
然后将混合好的铜浆刮涂到VC样品上，之后放入90℃~100℃的烘箱中烘烤20 min，将其溶剂烘干后，放入烧结炉里，先通入N2（氮气）并于450℃的条件下排胶90min，最后通入N2/H2，并在700 ℃~800 ℃的条件下烧结120 min，最终得到具有多孔毛细结构的VC样品。
实施例七
取平均粒径为10μm的电解铜粉和粒径为1000目的聚甲醛微球（POM微球）按7:1的质量比混合在一起，将该混合粉料加入质量分数为混合粉料的15%的聚乙烯醇缩丁醛PVB-乙二醇和异丁醇（体积比为5:1）的混合溶液中，并在混料机中充分搅拌后，依次加入质量分数为混合粉料的0.5%的增粘剂、质量分数为混合粉料的0.5%的分散剂、质量分数为混合粉料的1%的抗氧化剂以及上述铜浆中的其它组分，并继续搅拌0.5h ~6 h。
然后将混合好的铜浆刮涂到VC样品上，之后放入90℃~100℃的烘箱中烘烤20 min，将其溶剂烘干后，放入烧结炉里，先通入N2（氮气）并于500℃的条件下排胶90min，最后通入N2/H2，并在800 ℃~850 ℃的条件下烧结120 min，最终得到具有多孔毛细结构的VC样品。
实施例八
将粒径为500目、2000目和8000目的聚甲基丙烯酸甲酯微球按4:1:1的质量比混合组成复合粉料，取平均粒径为3μm的电解铜粉与复合粉料按7:1的质量比混合在一起，将该混合粉料加入质量分数为混合粉料的6%的乙烯基纤维素-1,2丁二醇与乙二醇（体积比为4:1）的混合溶液中，并在混料机中充分搅拌后，依次加入质量分数为混合粉料的0.5%的增粘剂、质量分数为混合粉料的0.5%的分散剂、质量分数为混合粉料的1%的抗氧化剂以及上述铜浆中的其它组分，并继续搅拌0.5h ~6 h。
然后将混合好的铜浆刮涂到VC样品上，之后放入90℃~110℃的烘箱中烘烤30 min，将其溶剂烘干后，放入烧结炉里，先通入N2并于450℃的条件下排胶90min，最后通入N2/H2，并在700 ℃~800 ℃的条件下烧结120 min，最终得到具有多孔毛细结构的VC样品。
实施例九
将粒径为300目、2000目和8000目的聚甲基丙烯酸甲酯微球按4:1:1的质量比混合组成复合粉料，取平均粒径为3μm的电解铜粉与复合粉料按7:1的质量比混合在一起，将该混合粉料加入质量分数为混合粉料的10%的乙烯基纤维素-1,2丁二醇与1,2-丙二醇（体积比为1:1）的混合溶液中，并在混料机中充分搅拌后，依次加入质量分数为混合粉料的0.5%的增粘剂、质量分数为混合粉料的0.5%的分散剂、质量分数为混合粉料的1%的抗氧化剂以及上述铜浆中的其它组分，并继续搅拌0.5h ~6 h。
然后将混合好的铜浆刮涂到VC样品上，之后放入90℃~110℃的烘箱中烘烤30 min，将其溶剂烘干后，放入烧结炉里，先通入N2并于450℃的条件下排胶90min，最后通入N2/H2，并在700 ℃~800 ℃的条件下烧结120 min，最终得到具有多孔毛细结构的VC样品。
实施例十
将粒径为300目、3000目和12000目的聚甲基丙烯酸甲酯微球按4:2:1的质量比混合组成复合粉料，取平均粒径为3μm的电解铜粉与复合粉料按8:1的质量比混合在一起，将该混合粉料加入质量分数为混合粉料的8%的聚乙烯醇-1,2丁二醇与异丁醇（体积比5:1）的混合溶液中，并在混料机中充分搅拌后，依次加入质量分数为混合粉料的0.5%的增粘剂、质量分数为混合粉料的0.5%的分散剂、质量分数为混合粉料的1%的抗氧化剂以及上述铜浆中的其它组分，并继续搅拌0.5h ~6 h。
然后将混合好的铜浆刮涂到VC样品上，之后放入90℃~110℃的烘箱中烘烤30 min，将其溶剂烘干后，放入烧结炉里，先通入N2并于450℃的条件下排胶90min，最后通入N2/H2，并在700 ℃~800 ℃的条件下烧结120 min，最终得到具有多孔毛细结构的VC样品。
以上所述仅为本发明的实施例，并非因此限制本发明的专利范围，凡是利用本发明说明书及附图内容所作的等效结构或等效流程变换，或直接或间接运用在其它相关的技术领域，均同理包括在本发明的专利保护范围内。

Claims (12)

  1. 一种用于印刷毛细结构的铜浆，其特征在于，所述铜浆由铜粉、高分子聚合物、溶剂、粘结剂、分散剂、流平剂、增粘结以及抗氧化剂组成，所述铜粉的粒径范围为0.5μm ~10μm，所述高分子聚合物的微球粒径为1μm ~50μm。
  2. 如权利要求1所述的用于印刷毛细结构的铜浆，其特征在于，所述高分子聚合物的微球粒径为300目~1000目、1000目~3000目以及5000目~12000目中的一种或多种，所述高分子聚合物的孔隙率为35%~75%。
  3. 如权利要求1所述的用于印刷毛细结构的铜浆，其特征在于，所述高分子聚合物为聚甲基丙烯酸甲酯、聚甲基丙烯酸异丁酯、甲基丙烯酸甲酯-甲基丙烯酸异丁酯共聚物、聚甲醛、聚氨酯以及聚苯乙烯中的一种或多种。
  4. 如权利要求1所述的用于印刷毛细结构的铜浆，其特征在于，所述溶剂为乙醇、丙醇、异丙醇、正丁醇、乙二醇、1,2-丙二醇、1,2-丁二醇、1,4-丁二醇以及水中的一种或多种。
  5. 如权利要求1所述的用于印刷毛细结构的铜浆，其特征在于，所述粘结剂为聚乙烯吡咯烷酮PVP、聚乙烯醇PVA、聚乙烯缩丁醛PVB、聚氨酯、羟甲基纤维素以及乙基纤维素中的一种或多种。
  6. 如权利要求1所述的用于印刷毛细结构的铜浆，其特征在于，所述分散剂为甲基戊醇、纤维素衍生物、聚丙烯酰胺以及脂肪酸聚乙二醇酯中的一种或多种。
  7. 如权利要求1所述的用于印刷毛细结构的铜浆，其特征在于，所述流平剂为十二烷基硫酸钠、十二烷基苯磺酸钠、十四烷基磺酸钠、十六烷基磺酸钠、卵磷脂、三乙醇胺、KH550、聚乙二醇、三乙醇胺、吐温80以及司盘80中的一种或多种。
  8. 如权利要求1所述的用于印刷毛细结构的铜浆，其特征在于，所述增粘剂为高粘度树脂，所述高粘度树胶为天然橡胶、丁苯橡胶、氯丁橡胶、C5以及C9类石油树脂中的一种或多种。
  9. 如权利要求1所述的用于印刷毛细结构的铜浆，其特征在于，所述抗氧化剂为柠檬酸、植酸、维生素、草酸、抗坏血酸以及葡萄糖中的一种或多种。
  10. 如权利要求1所述的用于印刷毛细结构的铜浆，其特征在于，所述铜粉与所述高分子聚合物的质量比为8~9:1，所述溶剂的质量分数为所述铜粉与所述高分子聚合物混合后的1%~70%，所述粘结剂的质量分数为所述铜粉与所述高分子聚合物混合后的0.1%~30%，所述分散剂的质量分数为所述铜粉与所述高分子聚合物混合后的0.01%~5%，所述流平剂的质量分数为所述铜粉与所述高分子聚合物混合后的0.01%~10%，所述增粘结的质量分数为所述铜粉与所述高分子聚合物混合后的0.01%~5%，所述抗氧化剂的质量分数为所述铜粉与所述高分子聚合物混合后的0.01%~10%。
  11. 如权利要求1所述的用于印刷毛细结构的铜浆，其特征在于，所述铜粉的平均粒径为3μm。
  12. 如权利要求1至11任意一项所述的用于印刷毛细结构的铜浆的制备方法，其特征在于，包括以下步骤：
    按所述铜浆的组分，先将所述高分子聚合物与所述铜粉混合均匀；
    之后再加入所述溶剂、所述粘结剂、所述分散剂、所述流平剂、所述增粘结以及所述抗氧化剂，并在混料机中充分搅拌0.5h~6h。
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