WO2020204361A1 - Feuille de blindage magnétique composite ayant d'excellentes fonctions de blindage et d'absorption d'ondes électromagnétiques et procédé de fabrication de feuille magnétique - Google Patents

Feuille de blindage magnétique composite ayant d'excellentes fonctions de blindage et d'absorption d'ondes électromagnétiques et procédé de fabrication de feuille magnétique Download PDF

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WO2020204361A1
WO2020204361A1 PCT/KR2020/002872 KR2020002872W WO2020204361A1 WO 2020204361 A1 WO2020204361 A1 WO 2020204361A1 KR 2020002872 W KR2020002872 W KR 2020002872W WO 2020204361 A1 WO2020204361 A1 WO 2020204361A1
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magnetic sheet
sheet
shielding
amorphous alloy
magnetic
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PCT/KR2020/002872
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English (en)
Korean (ko)
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김규진
배성관
권민호
김종수
정영미
한동화
안효배
최연수
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제닉스주식회사
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Priority claimed from KR1020190036574A external-priority patent/KR102080087B1/ko
Priority claimed from KR1020190036575A external-priority patent/KR102080088B1/ko
Application filed by 제닉스주식회사 filed Critical 제닉스주식회사
Publication of WO2020204361A1 publication Critical patent/WO2020204361A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
    • H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
    • H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
    • H01F1/12—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials
    • H01F1/14—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials metals or alloys
    • H01F1/147—Alloys characterised by their composition
    • 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
    • H05K9/00—Screening of apparatus or components against electric or magnetic fields

Definitions

  • the present invention relates to a composite magnetic shielding sheet having a function of shielding and absorbing electromagnetic waves, and more particularly, it is possible to shield and absorb electromagnetic waves that may cause harmful effects on the human body or malfunction of other electronic equipment. It relates to a composite magnetic shielding sheet capable of quickly discharging generated heat. In addition, the present invention relates to a method of manufacturing a magnetic sheet having excellent shielding and absorption and heat dissipation properties of electromagnetic waves capable of shielding and absorbing electromagnetic waves, as well as rapidly discharging heat generated from electronic devices.
  • Electromagnetic waves refer to electric and magnetic wavelengths including electric and magnetic fields generated by electric products or electronic products. Such electromagnetic waves may cause malfunctions of electrical and electronic devices. This is because electrical and electronic devices are recently mounted with high-density, high-integration circuit parts, etc. due to their small size, light weight, and thinness, causing radio wave disturbances between these circuit parts. .
  • electromagnetic waves affect not only the malfunction of electrical and electronic components, but also the human body.
  • electromagnetic waves may raise body temperature in whole or in part or stimulate the nervous system by electric currents induced in the body.
  • a coating layer for shielding electromagnetic waves is formed on a surface of an electronic component mounted in an electronic device as a method for blocking electromagnetic waves that have a harmful effect on such electronic products or human body.
  • electromagnetic interference EMI
  • electromagnetic compatibility Electric-Magnetic Interference
  • Korean Patent Registration No. 10-1803828 name of the invention: electromagnetic wave shielding sheet having flexural properties and a method for manufacturing the same
  • it is a combination of aluminum (Al) as a conductor and Sendust as an absorber.
  • Al aluminum
  • Sendust as an absorber.
  • It is a product having a thickness of less than 0.3mm manufactured, and has a very good shielding ability of 80dB or more, but has a disadvantage that the effective permeability drops sharply in the 20MHz band or more.
  • the amorphous alloy has a problem in that a significant amount of impurities are introduced into the powder during processing under the same conditions as the crystalline alloy, since the material in the grinding device and the ball is worn.
  • amorphous alloys are difficult to apply to shielding sheets because excellent soft magnetic properties (e.g., effective permeability, coercivity, iron loss, etc.) deteriorate significantly during processing, and accordingly, commercialization of shielding sheets as amorphous flake powder It is hardly being done.
  • excellent soft magnetic properties e.g., effective permeability, coercivity, iron loss, etc.
  • Patent Document 1 Korean Patent Registration No. 10-1803828 (announced on Dec. 4, 2017)
  • Patent Document 2 Republic of Korea Patent Publication No. 10-2018-0129721 (published on Dec. 5, 2018)
  • Patent Document 3 Korean Patent Application Publication No. 10-2007-0010428 (published on January 24, 2007)
  • Patent Document 4 Korean Patent Application Publication No. 10-2013-0096560 (published on August 30, 2013)
  • the objective of the present invention to easily powder the amorphous alloy ribbon through surface cracks or partial rearrangement of over-employed elements while maintaining the amorphous phase of the amorphous alloy ribbon.
  • the objective is to provide a method of manufacturing a magnetic sheet having excellent electromagnetic wave shielding and absorption and heat dissipation properties that can effectively absorb and shield electromagnetic waves even at a thin thickness by providing fine-grained amorphous alloy flakes in the form of a structure.
  • a magnetic sheet containing amorphous alloy powder of a plate-like structure subjected to nanocrystallization, and a magnetic sheet provided on the surface of the magnetic sheet It provides a composite electromagnetic wave shielding sheet comprising a conductive bonding means, and a soft magnetic alloy foil attached to the surface of the magnetic sheet through the adhesive.
  • a heat treatment step of heat-treating the amorphous alloy ribbon at a temperature below the crystallization temperature, and pulverizing the amorphous alloy ribbon to produce amorphous alloy flakes having an average particle diameter of 100 ⁇ m or less It provides a method of manufacturing a magnetic sheet excellent in shielding and absorption of electromagnetic waves and heat dissipation properties, including a pulverizing step of performing the amorphous alloy flake and a forming step of generating a magnetic sheet from the binder resin.
  • the composite magnetic shielding sheet according to the present invention provides a shielding rate of 85 dB or more in a frequency band of 100 kHz to 10 GHz, an absorption rate of 50% or more in a frequency band of 100 MHz to 10 GHz, and a thermal conductivity of 20 W/m ⁇ in the horizontal direction.
  • the above thermal conductivity can be provided.
  • the composite magnetic shielding sheet according to the present invention can effectively absorb and shield electromagnetic waves even in a thin thickness of 0.4 mm or less, it can be applied to various products such as the exterior of an electric control box with a lot of electromagnetic waves, mobile phones, and electronic components of smart cars. have.
  • the composite magnetic material shielding sheet according to the present invention can solve the problem of having a low shielding rate and absorption rate for electromagnetic waves in a high frequency band.
  • the amorphous alloy ribbon is heat-treated at a temperature lower than the crystallization temperature to maintain the amorphous phase, so that the surface crack or the partial rearrangement of the over-solidified elements can be proceeded.
  • the amorphous alloy ribbon can be easily powdered.
  • the magnetic sheet manufactured through the manufacturing method according to the present invention has a shielding rate of 30 dB or more, an absorption rate of 5% or more, a thermal conductivity of 1.0 W/m ⁇ or more in a vertical direction, and a thermal conductivity in the frequency band of 1 MHz to 10 GHz. Since is more than 4.0W/m ⁇ in the horizontal direction, it exhibits far superior electromagnetic wave shielding and absorption functions and heat dissipation properties than the shielding sheets of Sendust and FeSiCr alloys used in the past.
  • the magnetic sheet manufactured through the manufacturing method according to the present invention can effectively absorb and shield electromagnetic waves even in a thin thickness of 0.3 mm or less, the exterior of an electric control box with a lot of electromagnetic waves, mobile phones, electronic components of smart cars, etc. Can be applied to products.
  • FIG. 1 is a schematic diagram for explaining the configuration of a composite magnetic shielding sheet according to the present invention.
  • Figure 2 is a flow chart for explaining the manufacturing method of the composite magnetic shielding sheet according to the present invention.
  • Example 3 and 4 are SEM photographs showing the microstructure of the amorphous flake alloy powder used in Example 1.
  • FIG. 7 is a flowchart illustrating a method of manufacturing a magnetic sheet according to an embodiment of the present invention.
  • FIG. 8 is a flow chart for explaining a method of manufacturing a magnetic sheet according to another embodiment of the present invention.
  • a composite magnetic shielding sheet (hereinafter, abbreviated as a'composite magnetic shielding sheet') excellent in shielding and absorbing electromagnetic waves in Examples 1 to 4 of the present invention.
  • Examples 5 to 4 of the present invention In 9, a method of manufacturing a magnetic sheet (hereinafter, abbreviated as'magnetic sheet') having excellent shielding and absorption of electromagnetic waves and heat dissipation properties will be described.
  • the composite magnetic material shielding sheet according to the present invention includes a magnetic material sheet 10 provided with amorphous and nanocrystalline metal alloy flakes in a plate-like structure having absorption ability, and provided on the surface of the magnetic material sheet 10. It includes a conductive bonding means 20, and a soft magnetic alloy foil 30 attached by the adhesive.
  • the composite magnetic shielding sheet is 0.4 mm or less, preferably 0.15 mm or less so that it can provide sufficient shielding and absorption functions for electromagnetic waves while being applied to various products such as the exterior of an electric control box that generates many electromagnetic waves, mobile phones, and electronic components of smart cars. It is preferably formed to a thickness of 0.4mm.
  • the composite magnetic material shielding sheet according to the present invention includes a magnetic material sheet (10).
  • the magnetic sheet 10 is a sheet containing alloy powder having a plate-like structure therein, and further includes a binder resin.
  • the alloy powder having a plate-like structure may be an amorphous alloy powder of a heat-treated plate-like structure, or an alloy powder that has been heat-treated and nanocrystallized into a plate-like structure, or both.
  • the magnetic sheet 10 may be configured to include 100 parts by weight of an alloy powder having a plate-like structure and 6 to 10 parts by weight of a binder resin. At this time, if the content of the binder resin is less than 6 parts by weight, the binding strength of the binder resin is weak, and if the content of the binder resin exceeds 10 parts by weight, the shielding rate and the absorption rate of the magnetic sheet 10 decrease due to an excessive amount of the binder resin. do.
  • the heat-treated amorphous alloy powder of the plate-like structure and the alloy powder that has been heat-treated and nanocrystallized into a plate-like structure are all produced by heat-treating the amorphous alloy powder, and the amorphous alloy whose internal structure is capable of sintering nanocrystallization is nanocrystallized into a plate-like structure.
  • An amorphous alloy that becomes an alloy powder and the internal structure is not nanocrystallized becomes an amorphous alloy powder of a heat-treated plate-like structure.
  • the heat treatment is performed in order to remove internal stress generated during milling of the alloy powder and to improve soft magnetic properties.
  • the magnetic sheet 10 is formed to have a thickness of 0.1 mm to 0.3 mm. At this time, if the magnetic sheet 10 is formed with a thickness of 0.1 mm or less, it becomes difficult to provide sufficient electromagnetic wave absorption, and when the magnetic sheet 10 is formed with a thickness of more than 0.3 mm, the bendability of the composite magnetic shielding sheet is lowered. Can cause damage.
  • the magnetic sheet 10 is formed to have a density of 3.5 to 4.5 g/cm 2 . At this time, when the density of the magnetic sheet 10 is formed to be less than 3.5 g/cm 2 , the effective permeability is lowered to 85 or less in the frequency band of 10 MHz, and when the density is formed to exceed 4.5 g/cm 2 , the workability of hot forming There is a problem of falling.
  • the amorphous alloy powder of the plate-like structure preferably has an aspect ratio of 5 to 50 and an average thickness of 0.5 to 15 ⁇ m. This is because when the aspect ratio is 5 or less, the filling density is lowered, and when the aspect ratio exceeds 50, productivity is lacking. In addition, when the average thickness exceeds 15 ⁇ m, the effective permeability decreases due to the effect of the diamagnetic field in the high-frequency band, and when the average thickness is 0.5 ⁇ m or less, productivity and workability are deteriorated.
  • the alloy powder having a plate-like structure it is preferable to use an amorphous soft magnetic alloy powder containing iron or cobalt.
  • an amorphous soft magnetic alloy powder containing iron or cobalt Fe-Si-B-based, Fe-Nb-B-based, Fe-Si-CP-based, and the like may be used as the iron-based, and Co-Fe-B-based and the like may be used as the cobalt-based.
  • amorphous alloys such as FeSiBNbCu-based, FeSiCPCu-based, and FeNbB-based among the heat-treated plate-like amorphous alloy powders are prepared by performing heat treatment in a reducing atmosphere for 30 to 100 minutes at a temperature 10 to 50°C higher than the crystallization initiation temperature.
  • FeSiBNbCu system Fe 74 Si 13 B 9 Nb 3 Cu 1 , Fe 74 Si 13 B 9 Nb 5, etc. may be used
  • FeSiCPCu system Fe 78 Si 3 C 6 B 5 P 9 , Fe 85 Si 2 B 5 P 4 Cu 1 or the like may be used, and Fe 72 B 14 Si 10 Nb 5 may be used as the FeNbB system.
  • amorphous alloys such as FeSiB-based or CoFeB-based alloy powders that are heat treated above the crystallization initiation temperature and are not nanocrystallized into a plate-like structure are manufactured by performing heat treatment in a reducing atmosphere for 30 to 100 minutes at a temperature 20 to 50°C lower than the crystallization temperature. do.
  • FeSiB to step may be used such as Fe 78 Si 13 B 9
  • CoFeB to step may be used such as Co 70 Fe 5 Si 15 B 10 .
  • the binder resin is disposed so as to surround the outside of the alloy powder having a plate-like structure to provide insulation and a role of a binder, and a thermoplastic resin solution such as polyimide, PVA, urethane-based, or styrene-butadiene rubber (SBR) may be used.
  • a thermoplastic resin solution such as polyimide, PVA, urethane-based, or styrene-butadiene rubber (SBR) may be used.
  • SBR styrene-butadiene rubber
  • a binder resin in which 18% by weight of SBR solid powder and a small amount of a curing agent and a crosslinking agent are mixed may be used as the binder resin.
  • thermoplastic resin is useful for sheet compounding because the resin melts in the heat applied during lamination, and it becomes easy to attach the soft magnetic alloy foil 30 to one side of the magnetic sheet 10 without using a separate adhesive.
  • thermoplastic resin any one selected from the group consisting of polyimide resins, acrylic resins, and urethane resins may be used.
  • the composite magnetic material shielding sheet according to the present invention includes a conductive adhesive means (20).
  • the conductive adhesive means 20 is provided on the surface of the magnetic sheet 10 to provide an adhesive force so that the soft magnetic alloy foil 30 is attached to the magnetic sheet 10, the magnetic sheet 10 and the soft magnetic alloy foil It is located between (30).
  • This conductive bonding means 20 acts to improve the interlayer electrical conductivity between the magnetic sheet 10 and the soft magnetic alloy thin ribbon 30, thereby improving the vertical and horizontal thermal conductivity.
  • the conductive adhesive means 20 may be a conductive adhesive or a conductive double-sided tape, but is not limited thereto.
  • Silver conductive epoxy may be mainly used as the conductive adhesive, and a tape made of a conductive filler such as black carbon and graphite powder may be used as the conductive double-sided tape.
  • the composite magnetic material shielding sheet according to the present invention includes a soft magnetic alloy foil.
  • the soft magnetic alloy foil is attached to one side of the magnetic sheet 10 in a composite manner in order to utilize the properties of the soft magnetic material in the concept of magnetization, and is preferably formed to a thickness of 0.05 mm to 0.2 mm, but is not limited thereto. Does not. At this time, since the alloy thin ribbon, which is a soft magnetic material, is magnetized by an external magnetic field to efficiently absorb electromagnetic waves, the absorption rate of electromagnetic waves up to the high frequency band is improved.
  • an amorphous or crystalline alloy foil including iron or cobalt may be used as the soft magnetic alloy foil.
  • the soft magnetic amorphous alloy foil Fe-Si-B system, Fe-Si-B-Nb-Cu system, Co-Fe-B system, Fe-Nb-B system, etc. may be used.
  • the alloy foil Fe-Si-based, Fe-Ni-based, Fe-Ni-Mo-based, etc. may be used.
  • the present invention provides an effect of significantly improving the shielding rate and significantly improving the absorption rate compared to the case of using a non-magnetic metal foil using a soft magnetic alloy foil.
  • Figure 2 is a flow chart for explaining the manufacturing method of the composite magnetic shielding sheet according to the present invention.
  • the method of manufacturing a composite magnetic shielding sheet according to the present invention includes a first heat treatment step (S100) of heat-treating an amorphous alloy below a crystallization initiation temperature, and an alloy powder having a plate structure by pulverizing the heat-treated alloy.
  • S100 first heat treatment step
  • the first heat treatment step (S100) is a step of heat-treating the amorphous alloy at a temperature below the crystallization initiation temperature.
  • the amorphous alloy is easily pulverized by partially rearranging surface cracks or over-solvented elements while maintaining the amorphous phase. Let the flake progress.
  • the first heat treatment step (S100) it is preferable to perform the heat treatment for 30 to 100 minutes at a temperature of a reducing atmosphere 20 to 150 °C lower than the crystallization initiation temperature of the amorphous alloy.
  • the heat treatment temperature is between a temperature 20°C lower than the crystallization start temperature (ie, the crystallization start temperature to the crystallization start temperature -20°C), there is a concern that some crystallization may occur.
  • the heat treatment temperature is lower than 150°C based on the crystallization initiation temperature, the milling time exceeds 10 hours when manufacturing amorphous alloy powder having a plate-like structure with an average particle diameter of 100 ⁇ m or less. Incorporation of impurities may increase.
  • the heat treatment time is less than 30 minutes, sufficient heat treatment is not performed, and if the heat treatment time exceeds 100 minutes, the economy is poor.
  • the pulverizing step (S200) is a step of pulverizing the amorphous alloy heat-treated through the first heat treatment step (S100) to generate an amorphous alloy powder having a plate-like structure having an average particle diameter of 100 ⁇ m or less. It can be configured to include.
  • the plate-like amorphous alloy powder produced through the crushing step (S200) has a thickness of 0.5 ⁇ m to 15 ⁇ m, an average particle diameter of 10 ⁇ m to 100 ⁇ m, and an average aspect ratio (length/thickness) of 5 to 50.
  • the average particle diameter is less than 10 ⁇ m, it takes excessive milling time, and if it exceeds 100 ⁇ m, there may be a problem that the surface roughness is poor during sheet manufacturing.
  • the average aspect ratio is less than 5, the specific surface area of the amorphous alloy powder having a plate-like structure is small, so the molding density is lowered. If it exceeds 50, the average particle diameter of the amorphous alloy powder having a plate-like structure exceeds 100 ⁇ m and becomes coarse. A problem of poor surface roughness may occur.
  • the amorphous alloy heat-treated through the first heat treatment step (S100) is ground manually or by equipment such as a grinder.
  • the alloy powder pulverized through the crushing process is finely pulverized using a mill such as a ball mill or an attrition mill, and the plate structure To produce an alloy powder having
  • the milling speed of a mill is 300 to 600 rpm in the plate-like texture process. At this time, when the milling speed is less than 300 rpm, sufficient pulverization does not occur, and when the milling speed exceeds 600 rpm, a problem of increased wear in the device and the ball may occur due to the application of excessive energy.
  • the milling time of a mill is 3 to 10 hours in the process of forming a plate. At this time, if the milling time is less than 3 hours, it is difficult to manufacture a powder having an average particle diameter of 100 ⁇ m or less, and if it exceeds 10 hours, there may be a problem in that impurities are excessively mixed.
  • a solvent such as methanol, alcohol, and acetone may be used for a mill, such as an attention mill, in the process of forming a plate.
  • the weight ratio (solvent/powder) of the solvent and the powder (amorphous alloy ribbon) is 0.5 to 2.0. At this time, when the weight ratio of the solvent and the powder is less than 0.5, it is difficult to manufacture the amorphous alloy powder having a plate-like structure with a uniform surface, and when it exceeds 2.0, the manufacturing time of the amorphous alloy powder is excessively required.
  • the weight ratio (ball/powder) of the ball and powder used in the plate-like texture process based on the attention mill is 5-10. At this time, if the weight ratio is less than 5, milling time of 10 hours or more is required, and if the weight ratio exceeds 10, a problem of excessive wear due to direct collision with the balls may occur due to an excessive amount of input balls.
  • the second heat treatment step (S250) is a step of heat-treating the alloy powder having a plate structure in order to remove the stress inside the alloy powder due to the milling treatment and improve the soft magnetic properties of the alloy powder.
  • the heat treatment step (S250) is a nanocrystalline alloy such as Fe-Si-B-Nb-Cu-based, Fe-Si-CP-Cu-based, among fine-grained amorphous alloy powders generated through the pulverizing step (S200).
  • Heat treatment is performed in a reducing atmosphere for 30 to 100 minutes at a temperature 10 to 50°C higher than the silver crystallization initiation temperature, and an amorphous alloy such as Fe-Si-B or Co-Fe-B is 20 to 50°C above the crystallization initiation temperature.
  • Heat treatment is performed in a reducing atmosphere for 30 to 100 minutes at a low temperature.
  • the slurry generation step (S300) is a step of generating a slurry solution using a mixture of a metal powder having a plate-like structure that has passed through the heat treatment step (S250) and a binder resin and a solvent.
  • the solvent is added to the mixture to adjust the viscosity of the slurry together with the binder resin, and any one of water, alcohols, acetone, ether acetate, normal methylpyrrolidone, butyl cellosolve, and methylene chloride Alternatively, a mixture of these may be used.
  • a slurry solution having a viscosity of 5,000 to 10,000 cP is generated by adjusting the contents of the resin and solvent mixed in the mixture.
  • the viscosity is less than 5,000 cP, the magnetic sheet 10 is not formed because it is too thin, and if it exceeds 10,000 cP, a problem may occur in that the magnetic sheet 10 is cracked on the surface during the drying process.
  • This slurry solution is produced by adding 6 to 10 parts by weight of a binder resin and a solvent based on 100 parts by weight of the alloy powder having a plate structure. And the solvent is produced by mixing in a ratio of 4 to 10 times (weight ratio) than the binder resin. At this time, if the solvent is used less than 4 times, the movement of the alloy powder having a plate-like structure within the binder resin is restricted, and thus, the alloy powder having a plate-like structure in the magnetic sheet manufacturing step (S400) may not be arranged horizontally. have. In addition, when the solvent exceeds 10 times, there is a problem that the drying time increases when the magnetic sheet 10 is manufactured.
  • the content of the binder resin is less than 6% by weight, the binding strength of the binder resin is weakened, and if the content of the binder resin exceeds 10% by weight, the shielding rate and the absorption rate of the magnetic sheet 10 decrease due to the excessive amount of the binder resin. Occurs.
  • a magnetic sheet 10 having a thickness of 0.1 mm to 0.3 mm is generated with the slurry solution generated through the slurry generating step (S300).
  • the slurry solution is dried and the solvent present in the magnetic sheet 10 Volatilize. Then, the dried slurry is pressurized with a pressing device such as a press machine to produce a magnetic sheet 10 having a thickness of 0.30 mm or less, preferably 0.1 mm to 0.30 mm.
  • the slurry solution generated through the slurry generation step (S300) is applied on a release film, and then dried at a temperature in the range of 60 to 90°C, and then 120 to A magnetic sheet 10 having a density of 3.5 to 4.5 g/cm 2 is produced by molding at a pressure of 50 to 150 kgf/cm 2 on a hot press maintained at 175°C.
  • the molding temperature is less than 120°C
  • the binder is not sufficiently softened, resulting in a problem that the thickness of the sheet is uneven, and when it exceeds 175°C, the binder resin is dissolved.
  • the molding pressure is less than 50 kgf/cm 2, sufficient sheet molding density does not come out, and if it exceeds 150 kgf/cm 2 , damage to the sheet due to overpressure may occur.
  • the magnetic sheet 10 is cut to a specified standard through a tape casting method.
  • the tape casting method is a method of forming a sheet on a moving blade or a moving conveying film with a certain thickness according to the purpose.
  • the bonding means forming step (S500) is a step of providing a conductive bonding means 20 on one surface of the magnetic sheet 10 exposed to the outside, and applying a conductive bonding means 20 or attaching a conductive double-sided tape. .
  • the attaching step (S600) is a step of in close contact with the soft magnetic alloy thin ribbon 30 to the conductive bonding means 20 provided on the magnetic sheet 10 through the bonding means forming step (S500), the magnetic sheet ( Attach the soft magnetic alloy thin ribbon 30 to the surface of 10).
  • the amorphous alloy powder (Fe 74 Si 13 B 9 Nb 3 Cu 1 ) having the plate-like structure was subjected to heat treatment at 520°C, which is 20°C higher than the crystallization initiation temperature, for 30 minutes in a reducing atmosphere of hydrogen gas to make nanocrystallization.
  • An alloy powder was prepared.
  • the slurry solution was uniformly applied on a release film to prepare a sheet, and then dried sufficiently at a temperature of 90°C to volatilize the solvent component.
  • the sheet was hot-formed at 100kgf/cm 2 for 1 minute through a hot press at 150° C. at which the binder softens to prepare a magnetic sheet.
  • a conductive adhesive [8330-19G, MG Chemical, Canada] was applied to the upper surface of the magnetic sheet to a thickness of 10 ⁇ m.
  • a composite magnetic shielding sheet having a thickness of 0.29 mm was prepared by attaching a soft magnetic amorphous alloy thin ribbon (Fe 74 Si 13 B 9 Nb 3 Cu 1 ) having a thickness of 35 ⁇ m on the conductive adhesive.
  • Nanocrystalline alloy Fe 74 Si 13 B 9 Nb 3 Cu 1
  • SBR resin 37.5 g 7.5 parts by weight
  • toluene 187.5 g were used instead of 50 g of SBR resin and 250 g of toluene.
  • a composite magnetic shielding sheet was prepared.
  • a magnetic shielding sheet was prepared in the same manner as in Example 1, but with a single magnetic sheet without a conductive adhesive and a soft magnetic alloy foil.
  • the average particle diameter, microstructure, thickness of the shielding sheet, permeability, shielding rate, effective permeability, and thermal conductivity of the shielding sheets prepared according to Examples 1 to 4 and Comparative Examples 1 and 2 were evaluated.
  • the average particle diameter of the amorphous and nanocrystalline alloy powder having a plate-like structure was measured with a particle size analyzer [Bettersize S2, K-One Nano, Korea], and the microstructure was photographed with HR-SEM [S-4800, Hitachi, Japan].
  • the thickness of the shielding sheet was measured with a vernier caliper [500181-30, Mitutoyo, Japan]
  • the shielding rate of the shielding sheet was measured with a network analyzer [ZVA40, Rohde & Schwarz, Germany]
  • the absorption rate was Precision Impedance Analyzer [4294A- CFG002, Agilent, USA].
  • the effective permeability of the shielding sheet was measured with an Impedance Analyzer [E4991A, Agilent, USA]
  • the thermal conductivity was measured with a thermal conductivity meter [LFA457, NETZCH, Germany] and the results are shown in [Table 1] and Figs. It is summarized in Figure 6.
  • FIG. 3 and 4 are SEM photographs showing the microstructure of the amorphous alloy powder used in Example 1, and FIG. 5 is a graph showing the shielding rate for the shielding sheet manufactured through Examples and Comparative Examples, and FIG. 6 It is a graph showing the absorption rate for the shielding sheet manufactured through Examples and Comparative Examples.
  • the shielding rate of the composite magnetic shielding sheet of the present invention is 85 dB or more in the frequency band of 0.1 MHz to 10 GHz, and the absorption rate is 50% or more in the frequency band of 100 MHz to 10 GHz, It was confirmed that the thermal conductivity characteristic in the vertical direction was 30.0 W/m ⁇ or more, and the shielding rate, absorption rate, and thermal conductivity were significantly improved than when the magnetic sheet was used alone.
  • the electromagnetic wave incident on the shielding sheet is partially absorbed by the soft magnetic alloy foil attached to one side, and when the rest is reflected again, it is considered to be absorbed and dissipated again in the magnetic sheet.
  • the magnetic shielding sheet prepared in Comparative Example 2 has the same shielding rate as the magnetic shielding sheet of the present invention by attaching a metal foil made of Cu, but the effective permeability and absorption rate are lower. I could confirm that.
  • FIG. 7 is a flowchart illustrating a method of manufacturing a magnetic sheet according to the present invention.
  • the method of manufacturing a magnetic sheet according to the present invention includes a heat treatment step (S1000) of heat-treating an amorphous alloy ribbon, a grinding step (S2000) of pulverizing the heat-treated amorphous alloy ribbon, and pulverized amorphous alloy powder. And a molding step (S3000) of mixing a binder resin to generate a magnetic sheet.
  • the method of manufacturing a magnetic sheet according to the present invention includes a heat treatment step (S1000).
  • the heat treatment step (S1000) is a step of heat-treating the amorphous alloy ribbon at a temperature below the crystallization temperature, and pulverization and flakeization are easily progressed by partial rearrangement of surface cracks or over-solidified elements while maintaining the amorphous phase. .
  • the heat treatment for the amorphous alloy ribbon in the heat treatment step (S1000) is heat treated at a temperature exceeding the crystallization temperature of the amorphous alloy ribbon, the plate-like structure is not well formed in the process of grinding and flakeizing the amorphous alloy ribbon. There is a problem that the soft magnetic properties are greatly deteriorated due to non-uniform pulverization between crystal grains.
  • the amorphous alloy ribbon is preferably heat treated for 30 to 100 minutes at a temperature of a reducing atmosphere lower than the crystallization temperature of 20 to 150°C.
  • the heat treatment temperature is conducted between a temperature 20°C lower than the heat treatment temperature of the crystallization temperature, there is a concern that some crystallization may occur.
  • the heat treatment temperature is lower than 150°C based on the crystallization temperature, the milling time may exceed 10 hours when manufacturing amorphous alloy flakes having an average particle diameter of 100 ⁇ m or less, which may increase impurities in the powder. .
  • the heat treatment time is less than 30 minutes, sufficient heat treatment is not performed, and if the heat treatment time exceeds 100 minutes, the economy is poor.
  • an amorphous soft magnetic alloy ribbon containing iron-based or cobalt-based as such amorphous alloy ribbon.
  • FeSiB-based, FeNbB-based, FeSiCP-based, etc. may be used as the iron-based
  • CoFeB-based, etc. may be used as the cobalt-based.
  • the method of manufacturing a magnetic sheet according to the present invention includes a grinding step (S2000).
  • the pulverizing step (S2000) is a step of pulverizing an amorphous alloy ribbon to generate amorphous alloy flakes having an average particle diameter of 100 ⁇ m or less, and may include a pulverizing process and a flake forming process.
  • the amorphous alloy flake powder produced through the pulverization step (S2000) has an average particle diameter of 20 ⁇ m to 100 ⁇ m, and an average aspect ratio (length/thickness) of 5 to 20.
  • the average particle diameter is less than 20 ⁇ m, it takes excessive milling time, and if it exceeds 100 ⁇ m, there may be a problem that the surface roughness is poor during sheet manufacturing. And if the average aspect ratio is less than 5, the specific surface area of the amorphous alloy flake powder is small and the molding density is lowered. If it exceeds 20, the average particle diameter of the amorphous alloy flake powder exceeds 100 ⁇ m and becomes coarse, resulting in a problem of poor surface roughness of the sheet. Can be.
  • the amorphous alloy ribbon heat-treated through the heat treatment step (S1000) is pulverized manually or by equipment such as a pulverizer.
  • the amorphous alloy ribbon pulverized through the pulverization process is finely pulverized using a mill such as a ball mill or an attrition mill, and plate-shaped. It produces flake powder of tissue.
  • the milling speed of a mill is 300 to 600 rpm in the flake process. At this time, when the milling speed is less than 300 rpm, sufficient pulverization does not occur, and when the milling speed exceeds 600 rpm, a problem of increased wear in the device and the ball may occur due to the application of excessive energy.
  • the milling time of the mill is 3 to 10 hours in the flake process. At this time, if the milling time is less than 3 hours, it is difficult to manufacture a powder having an average particle diameter of 100 ⁇ m or less, and if it exceeds 10 hours, there may be a problem in that impurities are excessively mixed.
  • a solvent such as methanol, alcohol, and acetone may be used for a mill, such as an attention mill, in the flake process.
  • the weight ratio (solvent/powder) of the solvent and the powder (amorphous alloy ribbon) is 0.5 to 2.0. At this time, when the weight ratio of the solvent and the powder is less than 0.5, it is difficult to manufacture the flake powder having a flat surface structure, and when it exceeds 2.0, the manufacturing time of the flake powder is excessively required.
  • the weight ratio (ball/powder) of the ball and powder used in the flake process based on the attention mill is 5-10. At this time, if the weight ratio is less than 5, milling time of 10 hours or more is required, and if the weight ratio exceeds 10, a problem of excessive wear due to direct collision with the balls may occur due to an excessive amount of input balls.
  • FIG. 8 is a flow chart illustrating a method of manufacturing a magnetic sheet according to another embodiment of the present invention.
  • the method of manufacturing a magnetic sheet according to the present invention may further include a secondary heat treatment step (S2500) between the grinding step (S2000) and the forming step (S3000).
  • S2500 secondary heat treatment step between the grinding step (S2000) and the forming step (S3000).
  • the secondary heat treatment step (S2500) is a step of performing a heat treatment to remove stress in the amorphous alloy flake powder generated through the pulverization step (S2000) and increase the orientation of atoms in a direction that facilitates magnetization.
  • an amorphous alloy powder capable of sintering nanocrystallization such as FeSiBNbCu-based, FeSiCPCu-based, and FeNbB-based, among the fine-grained flake powders generated through the pulverizing step (S2000) is 10 than the crystallization temperature
  • Secondary heat treatment is carried out in a reducing atmosphere at a high temperature of ⁇ 50°C for 30 to 100 minutes, and amorphous alloys such as FeSiB-based or CoFeB-based, in which the internal structure is not nanocrystallized, have a temperature lower than the crystallization temperature of 20-50°C for 30 to 100 minutes
  • Secondary heat treatment is carried out in a reducing atmosphere. In this way, the temperature of the heat treatment is varied depending on whether or not the sintering of nanocrystallization is possible in order to improve the soft magnetic properties of the amorphous alloy flake powder.
  • FeSiBNbCu-based Fe 74 Si 13 B 9 Nb 3 Cu 1 , Fe 74 Si 13 B 9 Nb 5 etc. may be used, and FeSiCPCu-based Fe 78 Si 3 C 6 B 5 P 9 , Fe 85 Si 2 B 5 P 4 Cu 1 or the like may be used, and Fe 72 B 14 Si 10 Nb 5 may be used as the FeNbB system.
  • FeSiB-based Fe 78 Si 13 B 9 may be used, CoFeB-based Co 70 Fe 5 Si 15 B 10, etc. may be used.
  • the method of manufacturing a magnetic sheet according to the present invention includes a molding step (S3000).
  • the forming step (S3000) is a step of generating a magnetic sheet from an amorphous alloy flake powder and a binder resin, and includes a slurry forming process (S3100) and a sheet forming process (S3200).
  • a thermoplastic resin solution such as polyimide, PVA, urethane-based, and styrene-butadiene rubber (SBR) may be used for insulation and bonding between amorphous alloy flake powder.
  • a binder resin in which 18% by weight of SBR solid powder and a small amount of a curing agent and a crosslinking agent are mixed may be used.
  • this forming step (S3000) 100 parts by weight of the amorphous alloy flake powder and 6 to 10 parts by weight of the binder resin may be mixed. At this time, if the content of the binder resin is less than 6 parts by weight, the binding force of the binder resin is weakened, and if the content of the binder resin exceeds 10 parts by weight, the shielding rate and absorption rate of the magnetic sheet are deteriorated due to an excessive amount of the binder resin.
  • a slurry solution is produced by mixing amorphous alloy flake powder, a binder resin, and a solvent.
  • the slurrying process is a process of generating a slurry solution from a mixture of amorphous alloy flake powder, a binder resin, and a solvent.
  • a phosphate coating is treated to use an amorphous alloy flake provided with a phosphoric acid coating layer.
  • a slurry solution having a viscosity of 5,000 to 10,000 cP is produced by adjusting the contents of the resin and solvent mixed in the mixture.
  • the magnetic sheet is not formed because it is too thin, and if it exceeds 10,000 cP, the magnetic sheet may have a problem that cracks are formed on the surface during the drying process.
  • the solvent is added to the mixture to adjust the viscosity of the slurry together with the binder resin, and any one of water, alcohols, acetone, ether acetate, normal methylpyrrolidone, butyl cellosolve, methylene chloride, or these Mixtures of can be used.
  • This slurry solution is produced by adding 6 to 10 parts by weight of a binder resin and a solvent based on 100 parts by weight of the amorphous alloy flake powder. And the solvent is added in a ratio of 4 to 10 times (weight ratio) of the binder resin. At this time, if less than 4 times the solvent is used, the movement of the amorphous alloy flake powder within the binder resin is restricted, and thus a problem that the amorphous alloy flakes are not horizontally arranged in the sheet forming process (S3200) may occur. In addition, when the solvent exceeds 10 times, drying is difficult during manufacture of the magnetic sheet, resulting in an increase in drying time.
  • a magnetic sheet having a thickness of 0.3 mm or less is generated with the slurry solution generated through the slurry forming process (S3100).
  • a plurality of amorphous alloy flakes are horizontally arranged inside the magnetic sheet, and then the slurry solution is dried so that the solvent present in the magnetic sheet is volatilized. Then, the dried slurry is pressed with a pressing device such as a press machine to produce a magnetic sheet having a thickness of 0.30 mm or less, preferably 0.1 mm to 0.3 mm. At this time, if the dried slurry is less than 0.1mm, the absorption and shielding rate decreases, and if it exceeds 0.3mm, it lacks economic feasibility when applied to electrical components.
  • the slurry solution generated through the slurrying process (S3100) is applied on a release film, and then dried at a temperature in the range of 60 to 90°C, and then 120 to 175
  • a magnetic sheet having a density of 3.5 to 4.5 g/cm 2 is produced by molding at a pressure of 50 to 150 kgf/cm 2 on a hot press maintained at °C.
  • the molding temperature is less than 120°C
  • the binder is not sufficiently softened, resulting in a problem that the thickness of the sheet is uneven, and when it exceeds 175°C, the binder resin is dissolved.
  • the molding pressure is less than 50 kgf/cm 2
  • sufficient sheet molding density does not come out, and if it exceeds 150 kgf/cm 2 , damage to the sheet due to overpressure may occur.
  • the density is formed to be less than 3.5 g/cm 2
  • the effective permeability is lowered to 100 or less, and when the density is formed to exceed 4.5 g/cm 2 , there is a problem that the applied molding pressure exceeds 150 kgf/cm 2 .
  • the slurry solution is applied in a sheet shape, and then dried at a temperature of 50°C to 150°C for 5 to 20 minutes to volatilize the solvent present in the slurry solution.
  • the magnetic sheet is produced by applying a pressure of 1 to 10 tons/cm 2 at a temperature of 200 to 500°C with a pressing device such as a press machine.
  • the pressurization of the pressurization device may be repeatedly performed several times, and preferably, it may be repeatedly performed 1 to 2 times.
  • An amorphous alloy (Fe 74 Si 13 B 9 Nb 3 Cu 1 ) 1 kg with an average thickness of 20 ⁇ m and a width of 6 cm was placed at 460° C., which is 40° C. lower than the crystallization starting temperature of 500° C., under a hydrogen gas atmosphere. After the primary heat treatment for a minute, it was pulverized by hand to form 1 kg of amorphous alloy powder having an average particle diameter of 1 cm.
  • the amorphous alloy flake powder (Fe 74 Si 13 B 9 Nb 3 Cu 1 ) was subjected to a secondary heat treatment for 30 minutes under a reducing atmosphere of hydrogen gas at 520°C, a temperature 20°C higher than 500°C, a crystallization initiation temperature. I did.
  • the slurry solution was uniformly applied on a release film to prepare a sheet, and then dried sufficiently at a temperature of 75° C. to volatilize the solvent component.
  • a magnetic sheet having a thickness of 0.25 mm was prepared by hot forming the sheet at a temperature of 150° C. for softening the binder at 100 kgf/cm 2 for 1 minute through a hot press.
  • Example 5 In the same manner as in Example 5, a magnetic sheet was prepared using 30.0 g (6.0 parts by weight) of SBR resin and 150 g of toluene instead of 37.5 g of SBR and 187.5 g of toluene.
  • a magnetic sheet was prepared in the same manner as in Example 5, but using SBR 50.0g (10.0 parts by weight) and toluene 250g instead of SBR 37.5g and toluene 187.5g.
  • the average powder particle diameter, microstructure, thickness, density, permeability, shielding rate, and thermal conductivity of the magnetic sheet prepared according to Examples 5 to 9 and Comparative Examples 3 to 6 were evaluated.
  • the powder average particle diameter of the amorphous alloy flake powder was measured with a particle size analyzer [Bettersize S2, K-One Nano, Korea], and the microstructure was photographed with HR-SEM [S-4800, Hitachi, Japan].
  • the thickness of the magnetic sheet was measured with a vernier caliper [500-181-30, Mitutoyo, Japan]
  • the density was measured with a density meter [AS220, Radwag, Poland]
  • the crystallization temperature was measured with a differential thermal analyzer [STA8000, Perkin Elmer, USA].
  • the shielding rate of the magnetic sheet was measured with a network analyzer [ZVA40, Rohde & Schwarz, Germany], and the absorption rate was measured with a Precision Impedance Analyzer [4294A-CFG002, Agilent, USA].
  • thermal conductivity was measured with a thermal conductivity meter [LFA457, NETZCH, Germany], and the results are summarized in [Table 2] and FIGS. 9 to 12 below.
  • FIG. 9 is a graph showing the shielding rate for the magnetic sheet manufactured through the Example
  • FIG. 10 is a graph showing the shielding rate for the magnetic sheet manufactured through the Comparative Example
  • FIG. 11 is a magnetic body manufactured through the Example It is a graph showing the absorption rate of the sheet
  • FIG. 12 is a graph showing the absorption rate of the magnetic sheet manufactured through the comparative example.
  • the magnetic sheet of the present invention has a shielding rate of 30 dB or more from 1 MHz to 10 GHz frequency band, an absorption rate of 5% or more, and a thermal conductivity characteristic of 1.0 W/ in the vertical direction. It was confirmed that it was m ⁇ K or more, and the thermal conductivity characteristic in the horizontal direction was 4.0W/m ⁇ K or more.
  • the content of the binder resin is less than 6.0 parts by weight, the bonding strength with the binder resin is insufficient, resulting in lower molding density, resulting in a lower shielding rate. As it fell, it could be confirmed that the shielding rate, absorption rate, and heat dissipation characteristics fell.

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  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Electromagnetism (AREA)
  • Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Power Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Shielding Devices Or Components To Electric Or Magnetic Fields (AREA)
  • Soft Magnetic Materials (AREA)

Abstract

La présente invention concerne une feuille de blindage magnétique composite capable de protéger et d'absorber des ondes électromagnétiques qui peuvent provoquer des effets nocifs sur le corps humain ou le mauvais fonctionnement d'un autre équipement électronique et dissiper rapidement la chaleur générée dans des dispositifs électroniques et un procédé de fabrication d'une feuille magnétique. La présente invention concerne une feuille de blindage composite contre les ondes électromagnétiques et un procédé de fabrication d'une feuille magnétique ayant d'excellentes caractéristiques de protection contre et d'absorption des ondes électromagnétiques et de dissipation de chaleur, la feuille de protection composite contre les ondes électromagnétiques comprenant : une feuille magnétique comprenant une poudre d'alliage amorphe structuré de type plaque nanocristallisée ; une unité adhésive conductrice disposée sur une surface de la feuille magnétique ; et une bande mince d'alliage magnétique souple fixée à une surface de la feuille magnétique par l'intermédiaire d'un adhésif, et le procédé comprenant : une étape de traitement thermique consistant à traiter thermiquement un ruban d'alliage amorphe à une température inférieure à la température de cristallisation de celui-ci ; une étape de pulvérisation consistant à pulvériser le ruban d'alliage amorphe pour produire une poudre de flocon d'alliage amorphe ayant une longueur de 100 µm ou moins ; et une étape de moulage consistant à produire une feuille magnétique à partir de la poudre de flocon d'alliage amorphe et d'une résine de liant.
PCT/KR2020/002872 2019-03-29 2020-02-28 Feuille de blindage magnétique composite ayant d'excellentes fonctions de blindage et d'absorption d'ondes électromagnétiques et procédé de fabrication de feuille magnétique WO2020204361A1 (fr)

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KR1020190036574A KR102080087B1 (ko) 2019-03-29 2019-03-29 전자파의 차폐 및 흡수와 방열 특성이 우수한 자성체시트의 제조방법
KR1020190036575A KR102080088B1 (ko) 2019-03-29 2019-03-29 전자파의 차폐 및 흡수 기능이 우수한 복합 자성체 차폐시트
KR10-2019-0036574 2019-03-29
KR10-2019-0036575 2019-03-29

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JPS5917496B2 (ja) * 1973-12-24 1984-04-21 日本電子株式会社 走査電子顕微鏡等における焦点合わせ方法及びそのための装置
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JP2004140322A (ja) * 2002-08-20 2004-05-13 Alps Electric Co Ltd 電波吸収体及び電波吸収体の製造方法
KR101232222B1 (ko) * 2011-10-26 2013-02-12 한국기계연구원 전자파 흡수용 복합막 및 이의 제조방법
KR101399022B1 (ko) * 2012-12-27 2014-05-27 주식회사 아모센스 전자파 흡수시트 및 그의 제조방법과 이를 포함하는 전자기기
KR102080088B1 (ko) * 2019-03-29 2020-02-24 제닉스주식회사 전자파의 차폐 및 흡수 기능이 우수한 복합 자성체 차폐시트
KR102080087B1 (ko) * 2019-03-29 2020-02-24 제닉스주식회사 전자파의 차폐 및 흡수와 방열 특성이 우수한 자성체시트의 제조방법

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5917496B2 (ja) * 1973-12-24 1984-04-21 日本電子株式会社 走査電子顕微鏡等における焦点合わせ方法及びそのための装置
JP2001053485A (ja) * 1999-08-11 2001-02-23 Ntt Advanced Technology Corp 電磁波吸収シート
JP2004140322A (ja) * 2002-08-20 2004-05-13 Alps Electric Co Ltd 電波吸収体及び電波吸収体の製造方法
KR101232222B1 (ko) * 2011-10-26 2013-02-12 한국기계연구원 전자파 흡수용 복합막 및 이의 제조방법
KR101399022B1 (ko) * 2012-12-27 2014-05-27 주식회사 아모센스 전자파 흡수시트 및 그의 제조방법과 이를 포함하는 전자기기
KR102080088B1 (ko) * 2019-03-29 2020-02-24 제닉스주식회사 전자파의 차폐 및 흡수 기능이 우수한 복합 자성체 차폐시트
KR102080087B1 (ko) * 2019-03-29 2020-02-24 제닉스주식회사 전자파의 차폐 및 흡수와 방열 특성이 우수한 자성체시트의 제조방법

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