WO2021115096A1 - Nanomatériau composite de moulage et procédé de préparation associé, ensemble boîtier, et dispositif électronique - Google Patents

Nanomatériau composite de moulage et procédé de préparation associé, ensemble boîtier, et dispositif électronique Download PDF

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WO2021115096A1
WO2021115096A1 PCT/CN2020/130328 CN2020130328W WO2021115096A1 WO 2021115096 A1 WO2021115096 A1 WO 2021115096A1 CN 2020130328 W CN2020130328 W CN 2020130328W WO 2021115096 A1 WO2021115096 A1 WO 2021115096A1
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nano
composite material
injection
zone
injection composite
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PCT/CN2020/130328
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English (en)
Chinese (zh)
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杨鑫
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Oppo广东移动通信有限公司
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/06—Polystyrene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00—Making granules
    • B29B9/02—Making granules by dividing preformed material
    • B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08L71/12—Polyphenylene oxides
    • C08L71/126—Polyphenylene oxides modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets

Definitions

  • This application relates to the technical field of rice injection molding materials, in particular to a nano-injection composite material and a preparation method thereof, a housing assembly and an electronic device.
  • Nano Molding Technology is a technology that injects plastic directly onto the metal surface to achieve a perfect bond with the metal.
  • some nano-injection materials have been widely used in electronic and telecommunications applications to manufacture antennas, radio frequency (RF) components and other related equipment structural or functional components.
  • RF radio frequency
  • the existing nano injection molding materials generally have the shortcomings of high dielectric constant (Dk) and high dielectric loss factor (Dissipation Factor, Df), which seriously affect the bandwidth of the antenna, and cannot meet the future 5G communication requirements for long wavelengths and high wavelengths. Frequency and large capacity requirements.
  • This application provides a nano-injection composite material and its preparation method, housing assembly and electronic equipment; it can solve the common shortcomings of high dielectric constant and high dielectric loss factor of nano-injection material, and seriously affect the bandwidth of the antenna, which cannot meet the requirements The problem of long wavelength, high frequency and large capacity requirements.
  • the technical solution is as follows:
  • this application provides a nano-injection composite material, including the following components: crystalline resin, glass fiber, toughening agent, antioxidant, and lubricant; the crystalline resin includes syndiotactic polystyrene , One or more of polyethylene terephthalate and modified polyphenylene ether.
  • this application provides a method for preparing a nano-injection composite material, which includes the following steps:
  • the crystalline resin, toughening agent, antioxidant, and lubricant are mixed and then transferred to an extruder to be melted to obtain a mixture.
  • the crystalline resin includes syndiotactic polystyrene, polyethylene terephthalate and One or more of modified polyphenylene ether;
  • glass fiber is added to the mixture, and then granulated by melt extrusion to prepare a nano-injection composite material.
  • the present application provides a housing assembly, including a metal housing body and the nano-injection composite material as described in the first aspect of the application, and the nano-injection composite material interacts with the metal shell through nano-injection. Combination of body and body.
  • the present application also provides an electronic device, including the housing assembly described in the third aspect of the present application, and a display device, and the display device is connected to the housing assembly.
  • Figure 1 is a process flow diagram of a method for preparing a nano-injection composite material provided by an embodiment of the present application
  • FIG. 2 is a partial cross-sectional view of a housing assembly 100 provided by an embodiment of the present application
  • FIG. 3 is a cross-sectional view along the A-A direction of a housing assembly 100 provided by an embodiment of the present application;
  • FIG. 4 is a partial enlarged view of the cross-sectional view along the A-A direction of the housing assembly 100 provided by the embodiment of the present application in FIG. 3;
  • FIG. 5 is an actual structure diagram of a nano-hole on the surface of a metal casing body provided by an embodiment of the present application, and the scale is 500 nm;
  • FIG. 6 is a schematic structural diagram of an electronic device 200 provided by an embodiment of the present application.
  • FIG. 7 is a surface effect diagram of different nano-injection composite materials provided by the embodiments of the present application after an anode process.
  • the embodiment of the application provides a nano-injection composite material, including the following components: crystalline resin, glass fiber, toughening agent, antioxidant and lubricant; the crystalline resin includes syndiotactic polystyrene, polystyrene One or more of ethylene terephthalate and modified polyphenylene ether.
  • the mass fraction of the crystalline resin is 50-70%
  • the mass fraction of the glass fiber is 10-30%
  • the mass fraction of the toughening agent is 1-10%
  • the mass fraction of the antioxidant is The fraction is 0.1-1%
  • the mass fraction of the lubricant is 0.2-1%.
  • the glass fiber includes the following components in mass fraction: silica 50-60%, alumina 10-15% and boron oxide 20-30%; at a frequency of 1-10 GHz, the medium of the glass fiber
  • the electric constant is 4.0-4.5, and the dielectric loss factor is lower than 0.001.
  • the length of the glass fiber is 2.5-4.5 mm, and the diameter is 7-14 ⁇ m.
  • the nano-injection composite material further includes hollow glass microspheres, and the mass fraction of the hollow glass microspheres is 5-20%.
  • the total mass fraction of the glass fibers and the hollow glass beads in the nano-injection composite material is 18-35%, and the mass ratio of the glass fibers and the hollow glass beads is (1-5 ):1.
  • the volume of the internal cavity of the hollow glass microspheres accounts for 70-85%.
  • the particle size D50 of the hollow glass beads is 15-25 ⁇ m, and the compressive strength of the hollow glass beads is greater than 15000 psi.
  • the surface of the glass fiber is also coated with a coupling agent, and the coupling agent is a silane coupling agent.
  • the dielectric constant of the nano-injection composite material is less than 2.70, and the dielectric loss factor is less than 0.003.
  • the nano injection molding composite material is used for nano injection molding on the metal surface, and the bonding strength between the nano injection molding composite material and the metal is greater than 7 MPa.
  • the toughening agent includes one or two of ethylene-glycidyl methacrylate copolymer and styrene-butadiene-styrene block copolymer.
  • a heat stabilizer is also included, and the heat stabilizer includes one or more of zinc oxide, zinc sulfide, magnesium oxide, and zinc phosphate.
  • the embodiment of the application also provides a method for preparing the nano-injection composite material, which includes the following steps:
  • the crystalline resin, toughening agent, antioxidant, and lubricant are mixed and then transferred to an extruder to be melted to obtain a mixture.
  • the crystalline resin includes syndiotactic polystyrene, polyethylene terephthalate and One or more of modified polyphenylene ether;
  • glass fiber is added to the mixture, and then granulated by melt extrusion to prepare a nano-injection composite material.
  • the hollow glass microspheres are continuously added to the mixture.
  • the extruder is provided with five heating zones during the melt extrusion and granulation process, which are zone 1, zone 2, zone 3, zone 4, and zone 5.
  • the temperature settings are as follows: the first zone 70- 100°C, the second zone 240-250°C, the third zone 270-280°C, the fourth zone 280-300°C and the fifth zone 290-310°C, the die temperature of the extruder It is 290-310°C.
  • the embodiments of the present application also provide a housing assembly, including a metal housing body and the nano-injection composite material provided in the above-mentioned embodiments of the application, and the nano-injection composite material is combined with the metal housing body by nano-injection. .
  • the surface of the metal shell body and the surface combined with the nano injection molding composite material are provided with nano holes, the nano holes are filled with the nano injection molding composite material, and the diameter of the nano holes is 20-40 nm.
  • the housing assembly includes at least one of a middle frame and a rear cover.
  • An embodiment of the present application also provides an electronic device, including the housing assembly provided in the foregoing embodiment of the present application, and a display device, and the display device is connected to the housing assembly.
  • a nano injection molding composite material includes the following components: crystalline resin, glass fiber, toughening agent, antioxidant, and lubricant; the crystalline resin includes syndiotactic polystyrene ( One or more of sPS), polyethylene terephthalate (PET) and modified polyphenylene ether (MPPO).
  • crystalline resin includes syndiotactic polystyrene ( One or more of sPS), polyethylene terephthalate (PET) and modified polyphenylene ether (MPPO).
  • the nano-injection composite material described in this application is a composite material that can be applied to nano-injection technology.
  • the crystalline resin (or crystalline plastic) means that the polymer chains are ordered neatly, there is a decomposition process from nuclei to spherulites during the coagulation process, and the polymer chains are ordered according to the same pattern; Among them, the regularly arranged area is called the crystal area, the disordered area is called the amorphous area, and the percentage of the crystal area is called the crystallinity. Generally, the crystallinity of the crystalline resin (or crystalline plastic) is above 80%.
  • the crystalline resin described in this application is selected from polymer materials with low dielectric constant and low dielectric loss factor, and compared to the crystalline resin, compared to the traditional non-crystalline resin, it is more capable of interacting with metals. Form a stable integrated structure.
  • the crystalline resin is syndiotactic polystyrene, or polyethylene terephthalate, or modified polyphenylene ether. In another embodiment, the crystalline resin is composed of one or two of polyethylene terephthalate and modified polyphenylene ether, and syndiotactic polystyrene.
  • the benzene ring groups in the syndiotactic polystyrene are alternately distributed on both sides of the carbon main chain.
  • the syndiotactic polystyrene described in this application can be, but is not limited to, selected from a class of syndiotactic polystyrene polymers with a dielectric constant of less than 2.5 and a dielectric loss factor of less than 0.006 at a frequency of 1-10 GHz.
  • the mass fraction of the crystalline resin is 50-70%
  • the mass fraction of the glass fiber is 10-30%
  • the mass fraction of the toughening agent is 1-10%
  • the antioxidant The mass fraction of the lubricant is 0.1-1%, and the mass fraction of the lubricant is 0.2-1%.
  • the glass fiber includes the following components in mass fraction: 50-60% silica, 10-15% alumina and 20-30% boron oxide; at a frequency of 1-10 GHz, the The dielectric constant of the glass fiber is 4.0-4.5, and the dielectric loss factor is lower than 0.001.
  • the glass fiber of the component formula described in the present application has a lower dielectric constant, which is beneficial to reduce the dielectric properties of the nano-injection composite material described in the present application.
  • the glass fiber includes the following components in mass fraction: silica 50-60%, alumina 10-15%, boron oxide 20-30%, calcium oxide 4-8%, fluorine 1-2 % And the balance of the alkali metal oxide.
  • the alkali metal oxide may be, but not limited to, sodium oxide and potassium oxide.
  • the nano-injection composite material composed of components with a mass fraction ratio can exhibit low dielectric constant and low dielectric loss factor on the one hand, and can maintain a certain mechanical strength on the other hand.
  • the length of the glass fiber is 2.5-4.5 mm, and the diameter is 7-14 ⁇ m.
  • the glass fiber is chopped glass fiber.
  • the mechanical strength of the nano-injection composite material can be enhanced, and the rigidity and resistance of the nano-injection composite material can be improved. Impact capability.
  • the length of the glass fiber is 2.5-3.5 mm; the diameter of the glass fiber is 7-10 ⁇ m.
  • the length of the glass fiber is 3.0-4.0 mm; the diameter of the glass fiber is 10-14 ⁇ m.
  • the length of the glass fiber can be, but is not limited to, 2.5 mm, 2.8 mm, 3.0 mm, 3.2 mm, 3.5 mm, 3.8 mm, 4.0 mm, 4.1 mm, 4.3 mm, or 4.5 mm.
  • the diameter of the glass fiber may be, but is not limited to, 7 ⁇ m, 8 ⁇ m, 9 ⁇ m, 10 ⁇ m, 11 ⁇ m, 12 ⁇ m, 13 ⁇ m, or 14 ⁇ m.
  • the surface of the glass fiber is further coated with a coupling agent, and the coupling agent is a silane coupling agent.
  • the glass fiber wrapped with the coupling agent can be more stably fused in the nano-injection composite material to form a coupling with other components in the nano-injection composite material, which is beneficial to further improve its mechanical strength.
  • the nano-injection composite material further includes hollow glass microspheres, and the mass fraction of the hollow glass microspheres is 5-20%.
  • the volume ratio of the internal cavity of the hollow glass microspheres is 70-85%.
  • the volume ratio of the internal cavity mentioned herein refers to the ratio of the internal cavity of each hollow glass microsphere to the volume of the entire hollow glass microsphere.
  • the volume ratio of the internal cavity of the hollow glass beads is 75-85%.
  • the volume ratio of the internal cavity of the hollow glass beads is 80-85%.
  • the volume ratio of the internal cavity of the hollow glass microspheres may be, but not limited to, 70%, or 72%, or 75%, or 78%, or 80%, or 82%, or 85%.
  • the particle size D50 of the hollow glass beads is 15-25 ⁇ m, and the compressive strength of the hollow glass beads is greater than 15000 psi. In one embodiment, the particle size D50 of the hollow glass beads is 22-25 ⁇ m, and the compressive strength of the hollow glass beads is 15000-50000 psi.
  • the hollow glass microspheres in the compressive strength atmosphere can largely resist the risk of damage in participating in the preparation of nano-injection composite materials, and maintain a relatively balanced volume ratio and particle size of the hollow glass microspheres. status.
  • the volume ratio of hollow glass beads when increasing the volume ratio of hollow glass beads, it is necessary to increase the particle size of the hollow glass beads if the compressive strength of the hollow glass beads is to be maintained; and when the particle size of the hollow glass beads is reduced, the hollow glass beads
  • the volume ratio of the microbeads also needs to be reduced to keep the compressive strength of the hollow glass microbeads at a high level.
  • the hollow glass beads have a particle size D50 of 15-25 ⁇ m, a particle size D10 of 8-15 ⁇ m, and a particle size D90 of 30-50 ⁇ m.
  • the wall thickness of the hollow glass beads is 0.7-1.2 ⁇ m.
  • the bulk density of the hollow glass beads is 0.45-0.70 g/cm 3 .
  • the inner cavity of the hollow glass beads is filled with air.
  • Hollow glass beads with a high volume ratio in the internal cavity can further reduce the dielectric properties of the nano-injection composite material, reduce the value of the dielectric constant and the dielectric loss factor; at the same time, the hollow glass beads with high compressive strength can make The low dielectric properties of the injection molded composite material are more stable.
  • the sum of the mass fractions of the glass fibers and the hollow glass beads in the nano-injection composite material is 18-35%, and the mass ratio of the glass fibers and the hollow glass beads is (1 -5):1.
  • the glass fiber and the hollow glass beads with the mass ratio can greatly reduce the dielectric properties of the nano-injection composite material on the one hand, and on the other hand can make the nano-injection composite
  • the mechanical strength of the material is at a relatively high level.
  • the toughening agent includes one or two of ethylene-glycidyl methacrylate copolymer (EGMA) and styrene-butadiene-styrene block copolymer (SBS).
  • EGMA ethylene-glycidyl methacrylate copolymer
  • SBS styrene-butadiene-styrene block copolymer
  • the antioxidant includes a hindered phenolic antioxidant and/or a mixture of phosphite antioxidants.
  • the antioxidant described in the present application can prevent the resin component in the preparation process of the nano-injection composite material from being heated to cause molecular chain breakage, and affect the dielectric and mechanical properties of the nano-injection composite material.
  • the antioxidant is selected from two types: hindered phenolic antioxidant 1010 and phosphite antioxidant 168. Among them, hindered phenolic antioxidant 1010 is used as the main antioxidant, and phosphite Antioxidant 168 serves as an auxiliary antioxidant. For example, antioxidant B900.
  • the lubricant includes one or more of silicone masterbatch, pentaerythritol stearate (PETS) and ethylene bis fatty acid amide (EBS).
  • the lubricant is silicone masterbatch, or pentaerythritol stearate, or ethylene bis fatty acid amide.
  • the nano-injection composite material described in the present application further includes a thermal stabilizer, and the thermal stabilizer includes one or more of zinc oxide, zinc sulfide, magnesium oxide, and zinc phosphate.
  • the zinc phosphate is a compound that does not contain crystals.
  • the thermal stabilizer can prevent the components in the nano-injection composite material from undergoing a thermal decomposition process, and improve its thermal stability.
  • the dielectric constant of the nano-injection composite material is less than 2.70, and the dielectric loss factor is less than 0.003.
  • the dielectric constant of the nano-injection composite material is less than 2.55, and the dielectric loss factor is less than 0.003.
  • the nano-injection composite material is used for nano-injection injection on a metal surface, and the bonding strength between the nano-injection composite material and the metal is greater than 7 MPa. In one embodiment, the bonding strength between the nano-injection composite material and the metal is 7-30 MPa. In another embodiment, the bonding strength between the nano-injection composite material and the metal is 15-25 MPa.
  • the nano-injection composite material described in the present application has very low dielectric properties. At a frequency of 1GHz-10GHz, it has a low and stable dielectric constant and dielectric loss factor, which is much lower than that of the existing injection molding material, which is close to 3.
  • the electric constant value; meanwhile, the nano-injection composite material described in this application is a material that can be used for nano-injection.
  • the nano-injection composite material has high bonding strength with metal, has a stable structure, and is not easy to peel off.
  • another embodiment of the present application provides a method for preparing a nano-injection composite material, which includes the following steps:
  • the crystalline resin, toughening agent, antioxidant, and lubricant are mixed and then transferred to an extruder to be melted to obtain a mixture.
  • the crystalline resin includes syndiotactic polystyrene and polyethylene terephthalate.
  • the mass fraction of the crystalline resin is 50-70%, the mass fraction of the toughening agent is 1-10%, and the mass fraction of the antioxidant is 0.1 -1%, the mass fraction of the lubricant is 0.2-1%.
  • the mass fraction of the glass fiber is 10-30%.
  • the glass fiber is added after the other components are melted to form the mixture. Since the crystalline resin and other components have high hardness before they are completely melted, by delaying the addition of the glass fiber, it is possible to prevent the glass fiber from breaking a large amount during the mixing process of all the components, and the length becomes short, resulting in the nanometer The mechanical strength of the injection-molded composite material is weakened.
  • the mass fraction of the hollow glass beads is 5-20%.
  • the glass fiber and the hollow glass beads are added separately; and the hollow glass beads are also added after the other components are melted to form the mixture, which can effectively prevent the hollow glass beads from being Serious damage occurs during the mixing process; thereby affecting the dielectric properties of the material.
  • the glass fiber is first added to the mixture, and after being uniformly mixed, the hollow glass microbeads are added continuously.
  • the hollow glass microspheres are first added to the mixture, and after being uniformly mixed, the glass fibers are then added.
  • the extruder may, but is not limited to, be provided with a main feed port and two side feed ports, and the crystalline resin, toughening agent, antioxidant, and lubricant are mixed and passed through the main feed port.
  • the feed port is added to the extruder, melted, and then glass fiber is added from a side feed port close to the main feed port, and then the hollow glass microspheres are added from the other side feed port.
  • hollow glass microspheres are added from one side feeding port close to the main feeding port, and then the glass fiber is added from the other side feeding port.
  • the lubricant described in this application can reduce the friction between the components and the friction between the components and the barrel of the extruder; it is beneficial to efficiently obtain nano-injection composite materials and improve the quality of nano-injection composite materials. Reduce the phenomenon of wear of each component during the friction process.
  • the extruder is provided with five heating zones during the melt extrusion granulation process, which are zone 1, zone 2, zone 3, zone 4, and zone 5.
  • the temperature settings are as follows: 70-100°C, 240-250°C in the second zone, 270-280°C in the third zone, 280-300°C in the fourth zone, and 290-310°C in the fifth zone, the head of the extruder
  • the mold temperature is 290-310°C.
  • the specific morphology and extrusion rate of the nano-injection composite material can be adjusted during the actual production process, which is not specifically limited in this embodiment.
  • the preparation method provided in this embodiment is for the preparation method of the nano-injection composite material product described in the previous embodiment; in the preparation method, the specific definition of each component is the same as that of the nano-injection composite material product in the previous embodiment.
  • the descriptions of the points are the same, and will not be repeated in this embodiment.
  • the preparation method of the nano-injection composite material is simple in process, easy to operate, and can be used for large-scale industrial production.
  • the nano-injection composite material prepared by the preparation method has stable properties, very low dielectric properties, and has a low numerical value and stable dielectric constant and dielectric loss factor at a frequency of 1GHz-10GHz; at the same time, the The bonding strength between the nano-injection composite material and metal is high, the structure is stable, and it is not easy to peel.
  • the dielectric constant of the nano-injection composite material is even less than 2.55, and the dielectric loss factor is less than 0.003.
  • the nano-injection composite material described in the present application has excellent low dielectric properties, and the nano-injection composite material can form a stable integral molding structure with metal, it has high bonding strength with metal, and is a kind of outstanding performance. Nano injection molding materials; therefore, the nano injection molding composite materials described in this application have broad application prospects in the fields of electronics and telecommunications.
  • FIGS. 2 and 3 another embodiment of the present application provides a housing assembly 100, including a metal housing body 10 and a nano-injection composite material 11, and the nano-injection composite material 11 interacts with each other through nano-injection.
  • the metal shell body 10 is combined.
  • the specific definition of the nano-injection composite material 11 is consistent with the description of each component in the previous embodiment, and will not be repeated in this embodiment.
  • the metal may be but not metal aluminum, aluminum alloy, stainless steel or other alloy materials.
  • FIG. 4 is a partial enlarged view of the dashed circle in FIG. 3, wherein the surface of the metal shell body 10 and the surface of the nano injection molding composite material 11 are provided with nano holes 12, and the nano holes 12 It is filled with the nano-injection composite material 11, and the diameter of the nano-hole 12 is 20-40 nm.
  • the nano-holes 12 on the surface of the metal shell body 10 can be, but not limited to, obtained by etching. See FIG. 5, which is a scanning electron microscope image of the nano-holes formed on the surface of the aluminum alloy shell.
  • the nano-holes 12 on the surface of the metal shell body 10 are beneficial to realize the integral molding with the nano-injection composite material, and enhance the bonding force between the two.
  • the bonding strength between the metal shell body 10 and the nano-injection composite material 11 is greater than 7 MPa. In one embodiment, the bonding strength between the metal shell body 10 and the nano injection molded composite material 11 is 7-30 MPa. In another embodiment, the bonding strength between the metal shell body 10 and the nano-injection composite material 11 is 15-30 MPa.
  • the housing assembly 100 includes at least one of a middle frame and a rear cover.
  • the housing assembly 100 may also be a housing of other devices related to electronics and communication.
  • At least one of a USB hole, an earphone hole, a peripheral button hole, and an antenna slot is formed on the peripheral side frame of the housing assembly 100.
  • the nano-injection composite material described in this application has very low dielectric properties, it has a low and stable dielectric constant and dielectric loss factor at a frequency of 1 GHz-10 GHz; at the same time, the nano-injection composite material and metal High bonding strength, stable structure and not easy to peel off. Therefore, the housing assembly 100 containing the nano-injection composite material described in the present application can have a small impact on the signal bandwidth, meet the requirements of long wavelength, high frequency and large capacity, and can be widely used in the fields of electronics and communication technology, especially mobile terminals. .
  • FIG. 6 another embodiment of the present application provides an electronic device 200 that includes a housing assembly 100 and a display device 20, and the display device 20 is connected to the housing assembly 100.
  • the housing 100 includes a metal housing body 10 and a nano-injection composite material 11 combined with the metal housing body 10 by nano-injection.
  • the specific definition of the nano-injection composite material 11 is consistent with the description of each component in the previous embodiment, and will not be repeated in this embodiment.
  • the electronic device 200 further includes a back cover, and the material of the back cover is at least one of metal, plastic, and glass.
  • the electronic device 200 includes, but is not limited to, a mobile phone, a tablet computer, a notebook computer, a palmtop computer, a personal computer (PC), a personal digital assistant (PDA), and a portable media player (Portable Media Player, PMP), navigation devices, wearable devices, smart bracelets, pedometers and other mobile terminals, as well as fixed terminals such as digital TVs and desktop computers.
  • a mobile phone a tablet computer, a notebook computer, a palmtop computer, a personal computer (PC), a personal digital assistant (PDA), and a portable media player (Portable Media Player, PMP), navigation devices, wearable devices, smart bracelets, pedometers and other mobile terminals, as well as fixed terminals such as digital TVs and desktop computers.
  • PC personal computer
  • PDA personal digital assistant
  • PMP portable media player
  • PMP Portable Media Player
  • composition and comprehensive performance of the nano-injection composite material according to the embodiments of the present application will be described below through specific examples, wherein the comparative example is designed based on the embodiments of the present application.
  • Those skilled in the art will understand that the following embodiments are only used to illustrate the application, and should not be regarded as limiting the scope of the application.
  • specific techniques or conditions are not indicated in the examples, the procedures shall be carried out in accordance with the techniques or conditions described in the literature in the field or in accordance with the product specification.
  • the reagents or instruments used without the manufacturer's indication are all conventional products that can be purchased on the market.
  • a preparation method of nano injection molding composite material includes the following steps:
  • the temperature of the five heating zones of the extruder is set as follows: 70-100°C in the first zone, 240-250°C in the second zone , 270-280°C in three zones, 280-300°C in four zones, 290-310°C in five zones and 290-310°C in die head; then use pelletizing machine to cut the material strips into small plastic particles to obtain nano-injection composite Material; glass fiber length is about 3mm, diameter is about 7-14 ⁇ m; made of 52-56% SiO 2 , 12-15% Al 2 O 3 , 20-30% B 2 O 3 , 4-8% CaO, 1-2% It is composed of F and 1-2% (Li 2 O, Na 2 O, K 2 O); at a frequency of 1-10 GHz, the dielectric constant of the glass fiber is 4.0-4.5, and the dielectric loss factor is lower than 0.001.
  • a preparation method of nano injection molding composite material includes the following steps:
  • the temperature of the five heating zones of the extruder is set as follows: 70-100°C in the first zone, 240-250°C in the second zone , 270-280°C in three zones, 280-300°C in four zones, 290-310°C in five zones and 290-310°C in die head; then use pelletizing machine to cut the material strips into small plastic particles to obtain nano-injection composite Material; glass fiber length is about 3mm, diameter is about 7-14 ⁇ m; made of 52-56% SiO 2 , 12-15% Al 2 O 3 , 20-30% B 2 O 3 , 4-8% CaO, 1-2% It is composed of F and 1-2% (Li 2 O, Na 2 O, K 2 O); at a frequency of 1-10 GHz, the dielectric constant of the glass fiber is 4.0-4.5, and the dielectric loss factor is lower than 0.001.
  • a preparation method of nano injection molding composite material includes the following steps:
  • the temperature of the five heating zones of the extruder is set as follows: 70-100°C in the first zone, 240-250°C in the second zone , 270-280°C in three zones, 280-300°C in four zones, 290-310°C in five zones and 290-310°C in die head; then use pelletizing machine to cut the material strips into small plastic particles to obtain nano-injection composite Material; glass fiber length is about 3mm, diameter is about 7-14 ⁇ m; made of 52-56% SiO 2 , 12-15% Al 2 O 3 , 20-30% B 2 O 3 , 4-8% CaO, 1-2% It is composed of F and 1-2% (Li 2 O, Na 2 O, K 2 O); at a frequency of 1-10 GHz, the dielectric constant of the glass fiber is 4.0-4.5, and the dielectric loss factor is lower than 0.001.
  • a preparation method of nano injection molding composite material includes the following steps:
  • the temperature of the five heating zones of the extruder is set as follows: 70-100°C in the first zone, 240-250°C in the second zone , 270-280°C in three zones, 280-300°C in four zones, 290-310°C in five zones and 290-310°C in die head; then use pelletizing machine to cut the material strips into small plastic particles to obtain nano-injection composite Material; glass fiber length is about 3mm, diameter is about 7-14 ⁇ m; made of 52-56% SiO 2 , 12-15% Al 2 O 3 , 20-30% B 2 O 3 , 4-8% CaO, 1-2% It is composed of F and 1-2% (Li 2 O, Na 2 O, K 2 O); at a frequency of 1-10 GHz, the dielectric constant of the glass fiber is 4.0-4.5, and the dielectric loss factor is lower than 0.001.
  • a preparation method of nano injection molding composite material includes the following steps:
  • sPS-1 crystalline resin 3g of styrene-butadiene-styrene block copolymer toughening agent, antioxidant B900 0.2g, zinc phosphate heat stabilizer 0.3g, lubricant PETS 0.5g according to the ratio in advance Mix uniformly in the high-mixer, add the mixed materials from the main feed port at the back of the extruder, and melt; the direction from the main feed port to the die die is provided with a first side feed port and a second side in sequence Part feeding port;
  • zone temperature settings are as follows: zone one is 70-100°C, zone two is 240-250°C, zone three is 270-280°C, zone four is 280-300°C, zone five is 290-310°C, and the die is 290-310°C; Then use a pelletizer to cut the strips into small plastic particles to obtain nano-injection composite materials; the length of the glass fiber is about 3mm, and the diameter is about 7-14 ⁇ m; it is made of 52-56% SiO 2 , 12-15% Al 2 O 3 , 20 -30% B 2 O 3 , 4-8% CaO, 1-2% F and 1-2% (Li 2 O, Na 2 O, K 2 O) composition; under the frequency of 1-10GHz, the glass fiber
  • the dielectric constant is 4.0-4.5
  • a preparation method of nano injection molding composite material includes the following steps:
  • zone temperature settings are as follows: zone one is 70-100°C, zone two is 240-250°C, zone three is 270-280°C, zone four is 280-300°C, zone five is 290-310°C, and the die is 290-310°C; Then use a pelletizer to cut the strips into small plastic particles to obtain nano-injection composite materials; the length of the glass fiber is about 3mm, and the diameter is about 7-14 ⁇ m; it is made of 52-56% SiO 2 , 12-15% Al 2 O 3 , 20 -30% B 2 O 3 , 4-8% CaO, 1-2% F and 1-2% (Li 2 O, Na 2 O, K 2 O) composition; under the frequency of 1-10GHz, the glass fiber
  • the dielectric constant is 4.0-4.5
  • a preparation method of nano injection molding composite material includes the following steps:
  • zone temperature settings are as follows: zone one is 70-100°C, zone two is 240-250°C, zone three is 270-280°C, zone four is 280-300°C, zone five is 290-310°C, and the die is 290-310°C; Then use a pelletizer to cut the strips into small plastic particles to obtain nano-injection composite materials; the length of the glass fiber is about 3mm, the diameter is about 7-14 ⁇ m, and it is composed of 52-56% SiO 2 , 12-15% Al 2 O 3 , 20 -30% B 2 O 3 , 4-8% CaO, 1-2% F and 1-2% (Li 2 O, Na 2 O, K 2 O) composition; under the frequency of 1-10GHz, the glass fiber The dielectric constant is 4.0-4.5, and the dielectric constant is 4.0-4.5, and the dielectric constant is 4.0-4.5, and the dielectric constant is 4.0-4.5, and the dielectric constant is 4.0-4.5, and the dielectric constant is 4.0-4.5, and the dielectric constant is 4.0
  • a preparation method of nano injection molding composite material includes the following steps:
  • the temperature of the five heating zones of the extruder is set as follows: 70-100°C in the first zone, 240-250°C in the second zone , 270-280°C in three zones, 280-300°C in four zones, 290-310°C in five zones and 290-310°C in die head; then use pelletizing machine to cut the material strips into small plastic particles to obtain nano-injection composite Material; glass fiber length is about 3mm, diameter is about 7-14 ⁇ m; made of 52-56% SiO 2 , 12-15% Al 2 O 3 , 20-30% B 2 O 3 , 4-8% CaO, 1-2% It is composed of F and 1-2% (Li 2 O, Na 2 O, K 2 O); at a frequency of 1-10 GHz, the dielectric constant of the glass fiber is 4.0-4.5, and the dielectric loss factor is lower than 0.001.
  • a preparation method of nano injection molding composite material includes the following steps:
  • zone temperature settings are as follows: zone one is 70-100°C, zone two is 240-250°C, zone three is 270-280°C, zone four is 280-300°C, zone five is 290-310°C, and the die is 290-310°C; Then use a pelletizer to cut the strips into small plastic particles to obtain nano-injection composite materials; the length of the glass fiber is about 3mm, and the diameter is about 7-14 ⁇ m; it is made of 52-56% SiO 2 , 12-15% Al 2 O 3 , 20 -30% B 2 O 3 , 4-8% CaO, 1-2% F and 1-2% (Li 2 O, Na 2 O, K 2 O) composition; under the frequency of 1-10GHz, the glass fiber
  • the dielectric constant is 4.0-4.5
  • a preparation method of nano injection molding composite material includes the following steps:
  • zone temperature settings are as follows: zone one is 70-100°C, zone two is 240-250°C, zone three is 270-280°C, zone four is 280-300°C, zone five is 290-310°C, and the die is 290-310°C; Then use a pelletizer to cut the strips into small plastic particles to obtain nano-injection composite materials; the length of the glass fiber is about 3mm, and the diameter is about 7-14 ⁇ m; it is made of 74-78% SiO 2 , 0-1% Al 2 O 3 , 17 -22% B 2 O 3 , 0-2% CaO, 0-2% MgO and 3-5% (Li 2 O, Na 2 O, K 2 O) composition; under the frequency of 1-10GHz, the glass fiber The dielectric constant
  • a preparation method of nano injection molding composite material includes the following steps:
  • the heating zone temperature settings are as follows: Zone 1 70-100°C, Zone 2 240-250°C, Zone 3 270-280°C, Zone 4 280-300°C, Zone 5 290-310°C and the die of the machine head is 290-310°C ; Then use a pelletizer to cut the strips into small plastic particles to obtain nano-injection composite materials; the length of the glass fiber is about 3mm, and the diameter is about 7-14 ⁇ m; at a frequency of 1-10GHz, the dielectric constant of the glass fiber is 4.0- 4.5, the dielectric loss factor is less than 0.001; the particle size D50 of ordinary hollow glass beads is about 20 ⁇ m, the compressive strength is 35000psi, and the volume ratio of the internal cavity is 60%.
  • Table 1 The dielectric properties of the nano-injection composite material samples of each group of examples and comparative examples at 2.5 GHz, and the bonding strength with aluminum alloy
  • the nano-injection composite material samples prepared by the preparation methods described in Examples 1-7 of this application have a dielectric constant of less than 2.70 and a dielectric loss factor of less than 0.023 at a frequency of 2.5 GHz;
  • the dielectric constant at a frequency of 2.5 GHz is even lower than 2.53;
  • the nano-injection composite material sample prepared by the preparation method described in the examples in this application is combined with the aluminum alloy The strength is also relatively high. Among them, the bonding strength between the nano-injection composite material sample of Example 6 and the aluminum alloy reaches 17.4 MP.
  • the dielectric constant of the nano-injection composite material sample in Comparative Example 1-2 is relatively low at a frequency of 2.5 GHz, the bonding strength between it and the aluminum alloy is also very low, and it is not suitable as a nano-injection material;
  • the dielectric properties of the nano-injection composite materials described in 3-4 are all higher than those of Examples 1-6, and are generally higher than 2.71. Therefore, the low-dielectric crystalline resin raw materials, low-dielectric glass fibers, and hollow glass beads with a high volume ratio used in the preparation method described in this application can all help reduce the nanoinjection composite material.
  • the dielectric constant and the dielectric loss factor are of great significance to the design of communications and antennas, especially in 5G communications.
  • the nano-injection composite material sample described in this application has a high bonding strength with the aluminum alloy, and its integrated structure is stable. , It is not easy to peel off.
  • FIG. 7 the surface effect of the detector after the aluminum alloy plate containing different nano-injection composite materials is subjected to the anode process is shown in FIG. 7, where (a) in FIG. 7 is the nano-injection composite material prepared in Example 6 of the present application , Figure 7 (b) is the existing PBT material (Toray), model: 2107G-X07, Dk2.9, Df0.006; Sabic engineering plastics (Sabic), model: WF004N Dk2 .95, Df0.009); after the two were subjected to the anode process under the same conditions, it was found that the color of the nano-injection composite material prepared in Example 6 of the present application did not change, while the existing PBT material appeared white in color and had acid storage. Therefore, the nano-injection composite material prepared in Example 6 of the present application has higher stability performance, and is tightly combined with the aluminum alloy plate, and there is no acid storage phenomenon.
  • the nano-injection composite material sample of Example 5 has a dielectric constant of 2.487 at a frequency of 5.0 GHz and a dielectric loss factor of less than 0.00242; the nano-injection composite material of Example 6
  • the material sample has a dielectric constant of 2.541 at a frequency of 5.0 GHz and a dielectric loss factor of less than 0.00240.
  • the nano-injection composite material sample of Example 7 has a dielectric constant of 2.549 at a frequency of 5.0 GHz, and a dielectric loss factor of less than 0.00246.
  • Table 4 The dielectric performance test data table of the product prepared in Example 6 under high frequency

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Abstract

La présente invention concerne un nanomatériau composite de moulage, comprenant les composants suivants : une résine cristalline, une fibre de verre, un agent de trempe, un antioxydant et un lubrifiant. La résine cristalline comprend un ou plusieurs des éléments suivants : le polystyrène syndiotactique, le polyéthylène glycol téréphtalate et l'oxyde de polyphénylène modifié. Les problèmes, selon lesquels des nanomatériaux de moulage présentent généralement les défauts d'une constante diélectrique élevée et d'un facteur de dissipation diélectrique élevé, affectent gravement la largeur de bande des antennes et ne peuvent pas satisfaire aux exigences de longueur d'onde longue, de haute fréquence et de grande capacité, peuvent être résolus. La présente invention concerne en outre un procédé de préparation du nanomatériau composite de moulage, un ensemble boîtier et un dispositif électronique.
PCT/CN2020/130328 2019-12-13 2020-11-20 Nanomatériau composite de moulage et procédé de préparation associé, ensemble boîtier, et dispositif électronique WO2021115096A1 (fr)

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CN111793335A (zh) * 2020-08-20 2020-10-20 东莞市奥能工程塑料有限公司 一种低介电纳米注塑材料
CN112564661A (zh) * 2020-12-03 2021-03-26 广东广纳芯科技有限公司 改善声表面波滤波器膜层界面结合强度的方法
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