Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B15/00—Layered products comprising a layer of metal
  • B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
  • B32B15/013—Layered products comprising a layer of metal all layers being exclusively metallic one layer being formed of an iron alloy or steel, another layer being formed of a metal other than iron or aluminium
  • B32B15/015—Layered products comprising a layer of metal all layers being exclusively metallic one layer being formed of an iron alloy or steel, another layer being formed of a metal other than iron or aluminium the said other metal being copper or nickel or an alloy thereof
• • 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
  • H05K9/0073—Shielding materials
  • H05K9/0081—Electromagnetic shielding materials, e.g. EMI, RFI shielding
  • H05K9/0088—Electromagnetic shielding materials, e.g. EMI, RFI shielding comprising a plurality of shielding layers; combining different shielding material structure
• • 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
  • 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
  • H01F1/14708—Fe-Ni based alloys
• • 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
  • H01F1/153—Amorphous metallic alloys, e.g. glassy metals
  • H01F1/15316—Amorphous metallic alloys, e.g. glassy metals based on Co
• • 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
  • H05K9/0073—Shielding materials
  • H05K9/0075—Magnetic shielding materials
• • 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
  • H05K9/0073—Shielding materials
  • H05K9/0081—Electromagnetic shielding materials, e.g. EMI, RFI shielding
  • H05K9/0084—Electromagnetic shielding materials, e.g. EMI, RFI shielding comprising a single continuous metallic layer on an electrically insulating supporting structure, e.g. metal foil, film, plating coating, electro-deposition, vapour-deposition

Definitions

• the present invention relates to electromagnetic wave shielding materials, covering materials or exterior materials, and electric/electronic equipment.
• the DC current generated by the secondary battery is converted to AC current via an inverter and then supplied to the AC motor with the necessary power.
• an inverter In eco-friendly vehicles equipped with secondary batteries, such as electric vehicles and hybrid vehicles, the DC current generated by the secondary battery is converted to AC current via an inverter and then supplied to the AC motor with the necessary power. , many of which adopt a method of obtaining a driving force, and electromagnetic waves are generated due to the switching operation of the inverter.
• Electromagnetic waves are emitted not only from automobiles but also from many electrical and electronic devices, including communication devices, displays, and medical devices. Electromagnetic waves may cause malfunction of precision equipment, and there is also concern about the effects on the human body.
• a conductive layer such as copper typically exhibits good shielding properties against electromagnetic waves in a high frequency range (1 MHz or higher). However, in the low frequency range (less than 1 MHz), the shielding property against electromagnetic waves is low only with a conductive layer such as copper. are known to exhibit good shielding properties against
• Patent Literature 1 proposes the following technique. "A noise suppression sheet used to suppress noise of 1 MHz or less, comprising n magnetic layers having a magnetic layer (A 1 ) and a magnetic layer (A n ), and at least (n-1) layers of conductive a noise suppression layer having layers, wherein the magnetic layers and the conductive layers are alternately laminated;
• X i represented by the following formula (1) is 1 or more
• the sum of Xi of each magnetic layer is 4 or more and 15 or less
• a noise suppression sheet characterized in that each of the conductive layers has a proportionality constant of 4 or more obtained by linearly approximating the shielding properties of 0.2 to 1 MHz in magnetic field shielding measurement by the KEC method.
• n is an integer of 2 or more
• i is an integer of 1 or more and n or less
• ⁇ ′ i is the relative permeability of the magnetic layer (A i ) at 1 MHz
• t i is the magnetic layer (A i ).
• the noise suppression sheet described in Patent Document 1 shows high shielding performance in the low frequency range. However, depending on the product field, high shielding performance may be required in the region of about 100 kHz, while the noise suppression sheet described in Patent Document 1 mentions shielding performance at 300 kHz (Patent Document 1 [0110 ], [0111]), but no mention is made of shielding performance in the lower, low-frequency range. Therefore, it is unclear whether the noise suppression sheet described in Patent Document 1 has sufficient shielding performance in a low frequency range lower than 300 kHz, and the technology of Patent Document 1 still has room for improvement.
• an object of one embodiment of the present invention is to provide an electromagnetic wave shielding material with good shielding properties in the low frequency range.
• the present invention provides an electromagnetic wave shielding material having a structure in which a ferromagnetic layer and a nonmagnetic conductive metal layer are laminated, wherein at least one surface of the nonmagnetic conductive metal layer is coated with copper and
• the electromagnetic wave shielding material further has a treated film containing an alloy containing nickel.
• the structure has ferromagnetic layers laminated via at least two non-magnetic conductive metal layers.
• At least one of the outermost layers is a non-magnetic conductive metal layer.
• the alloy contained in the treated film further contains cobalt.
• the mass ratio of nickel in each treatment film is 1, the mass ratio of cobalt in each treatment film is 1.50 to 4.50.
• a covering material or an exterior material for electrical/electronic equipment comprising any one of the electromagnetic wave shielding materials described above.
• an electric/electronic device comprising the above covering material or exterior material.
• an electromagnetic wave shielding material with good shielding properties in the low frequency range.
• Electromagnetic shielding material One embodiment of the electromagnetic wave shielding material according to the present invention has a structure in which a ferromagnetic layer and a nonmagnetic conductive metal layer are laminated. Above all, in one embodiment, from the viewpoint of shielding properties, it is preferable that the ferromagnetic layers are laminated via at least two non-magnetic conductive metal layers. Furthermore, from the viewpoint of shielding properties, at least one outermost layer (uppermost layer and/or lowermost layer) of the electromagnetic wave shielding material is preferably a nonmagnetic conductive metal layer, and both of the outermost layers are nonmagnetic conductive metal layers. A metal layer is preferred.
• a treated film of an alloy containing copper and nickel is further provided on at least one surface of the non-magnetic conductive metal layer, and preferably both surfaces of the non-magnetic conductive metal layer further include the above-described treated film.
• the treatment film is preferably arranged with the ferromagnetic layer and the non-magnetic conductive metal layer interposed therebetween from the viewpoint of efficiently causing electromagnetic wave absorption/attenuation in the ferromagnetic layer.
• at least one of the outermost films (the uppermost film and/or the lowermost film) of the electromagnetic wave shielding material is preferably a treated film formed on a non-magnetic conductive metal layer.
• the treated film disposed between the ferromagnetic layer and the non-magnetic conductive metal layer includes not only the aspect formed on at least one surface of the non-magnetic conductive metal layer, but also the non-magnetic conductive metal layer. It also includes an embodiment formed on the surface of the ferromagnetic layer adjacent to the non-magnetic conductive metal layer side. Due to these configurations, the electromagnetic wave shielding material exhibits excellent shielding properties in the low frequency range. While not intending to limit the invention by theory, it is believed that this is for the following reasons. When the non-magnetic conductive metal layer is irradiated with electromagnetic waves, some of them pass through but some of them are reflected.
• the non-magnetic conductive metal layer when a ferromagnetic layer is sandwiched between two non-magnetic conductive metal layers, electromagnetic waves repeatedly reflected between the non-magnetic conductive metal layers (multiple reflection) are absorbed by the magnetic material, and the non-magnetic conductive metal layer A good shielding effect can be obtained as compared with a single substance or a single ferromagnetic material.
• at least one surface of the non-magnetic conductive metal layer is subjected to a roughening plating treatment to form a treated film containing an alloy containing Cu—Ni. It is possible to efficiently absorb and attenuate electromagnetic waves in the ferromagnetic layer by causing diffuse reflection instead of reflection.
• the ferromagnetic layer contains a material with high magnetic permeability, for example, a composite sheet in which resin is mixed and dispersed, a metal foil, and a laminate having a high magnetic permeability while laminating a resin sheet on at least one surface of the metal foil is mentioned.
• the ferromagnetic layer has a relative magnetic permeability of approximately 10 to 100,000. The relative magnetic permeability can be measured using a commercially available magnetic permeability measuring device.
• resins include natural resins and synthetic resins, and synthetic resins are preferred from the viewpoint of workability. These materials can also be mixed with fiber reinforcements such as carbon fibres, glass fibres, and aramid fibres.
• synthetic resins include polyesters such as PET (polyethylene terephthalate), PEN (polyethylene naphthalate) and PBT (polybutylene terephthalate), olefin resins such as polyethylene and polypropylene, polyamides, Polyimide, liquid crystal polymer, polyacetal, fluorine resin, polyurethane, acrylic resin, epoxy resin, silicone resin, phenol resin, melamine resin, ABS resin, polyvinyl alcohol, urea resin, polyvinyl chloride, PC (polycarbonate), polystyrene, styrene-butadiene rubber Among these, PET, PEN, polyamide, and polyimide are preferred for reasons of workability and cost.
• the synthetic resin can also be an elastomer such as urethane rubber, chloroprene rubber, silicone rubber, fluororubber, styrene, olefin, vinyl chloride, urethane, and amide.
• the synthetic resin itself may serve as an adhesive.
• the structure is such that non-magnetic conductive metal layers having a treated film formed on the surface are laminated via the adhesive.
• the adhesive is not particularly limited, but acrylic resin, epoxy resin, urethane, polyester, silicone resin, vinyl acetate, styrene butadiene rubber, nitrile rubber, phenol resin, cyanoacrylate, etc.
• the composite sheet can be laminated in a film-like or fibrous form.
• a composite sheet may be formed by applying an uncured resin composition to a non-magnetic conductive metal layer or treated film and then curing the composition. is preferred for reasons of ease of manufacture.
• a PET film can be preferably used.
• the strength of the electromagnetic wave shielding material can be increased.
• the ferromagnetic layer is a metal foil
• the ferromagnetic layer is a metal foil containing at least one selected from nickel, iron, permalloy (Ni—Fe alloy) and sendust (Fe—Si—Al alloy). is more preferable. Since these materials have relatively high magnetic permeability, it is possible to reduce the spatial magnetic field by collecting magnetic flux components contained in noise.
• the nonmagnetic conductive metal layer is made of a conductive metal material exhibiting diamagnetic or paramagnetic properties.
• the material of the non-magnetic conductive metal layer to be used is not particularly limited, but from the viewpoint of improving shielding properties against AC magnetic fields and AC electric fields, it is preferable to use metal materials with excellent conductivity.
• Such metals include aluminum, which has a conductivity of about 39.6 ⁇ 10 6 S/m, copper, which has a conductivity of about 58.0 ⁇ 10 6 S/m, and copper, which has a conductivity of about 61.4 ⁇ 10 6 S /m.
• S/m silver is mentioned. That is, the non-magnetic conductive metal layer preferably contains one selected from aluminum, copper and silver, and considering both conductivity and cost, it is practical to adopt aluminum or copper. more preferable.
• the nonmagnetic conductive metal layers used in the electromagnetic wave shielding material according to the present invention may all be the same metal, or different metals may be used for each layer. Alloys of the metals mentioned above can also be used.
• the shape of the non-magnetic conductive metal layer is not particularly limited, but metal foil is an example.
• copper foil is used as the non-magnetic conductive metal layer, the shielding properties are improved, so it is preferable that the copper foil has a high purity, and the purity is preferably 99.5% by mass or more, more preferably 99.8% by mass or more.
• the copper foil a rolled copper foil, an electrolytic copper foil, a metallized copper foil, or the like can be used, but a rolled copper foil having excellent flexibility and moldability is preferable.
• alloying elements are added to the copper foil to form the copper alloy foil, the total content of these elements and unavoidable impurities should be less than 0.5% by mass.
• a total of at least one selected from tin, manganese, chromium, zinc, zirconium, magnesium, nickel, silicon, and silver is 50 to 2000 mass ppm in total, and / or phosphorus is 10 to 50 mass ppm. If it contains ppm, it is preferable because elongation is improved as compared with a pure copper foil of the same thickness.
• the treated film contains an alloy containing copper and nickel formed on at least one surface of the non-magnetic conductive metal layer from the viewpoint of enhancing shielding properties.
• the treatment film may contain an alloy further containing cobalt in addition to copper and nickel.
• the treated film includes an electromagnetic wave absorption assisting film of an alloy containing at least copper and nickel, and further includes one or more selected from a heat-resistant film, an antirust film, and a weather-resistant film within a range that does not impair the effects of the present invention. may include.
• the electromagnetic wave absorption assisting film may be an alloy further containing cobalt in addition to copper and nickel.
• the organic coating film containing a silane coupling agent can be used as the base film and the silane coupling treated weather resistant film. That is, in addition to copper and nickel, the treated film may further contain one or more metals selected from cobalt, zinc, molybdenum, tin, phosphorus, tungsten, chromium and silicon.
• the treatment film interposed between the ferromagnetic layer and the non-magnetic conductive metal layer can improve adhesion between the ferromagnetic layer and the non-magnetic conductive metal layer. can also be increased.
• the electromagnetic wave absorption assisting film can be produced by known methods such as plating, metal vapor deposition, and sputtering. Among them, a method of forming an electromagnetic wave absorption assisting film containing copper and nickel by plating the surface of a non-magnetic conductive metal layer will be described below as an example.
• a particle film made of copper and nickel is formed on at least one surface of the non-magnetic conductive metal layer. , copper, cobalt and nickel.
• Platinum treatment conditions (roughening plating treatment) 1: copper and nickel alloy plating)
• An example of copper and nickel plating conditions is as follows. Liquid composition: 10 to 20 g/L of copper, 5 to 15 g/L of nickel pH: 2-3 Liquid temperature: 30-50°C Current density: 10-65A/ dm2 Coulomb amount: 10 to 50 As/dm 2
• plating treatment conditions (roughening plating treatment) 2: copper, cobalt and nickel alloy plating)
• An example of plating treatment conditions for copper, cobalt and nickel is as follows. Liquid composition: 10-20 g/L copper, 5-15 g/L cobalt, 5-15 g/L nickel pH: 2-3 Liquid temperature: 30-50°C Current density: 10-65A/ dm2 Coulomb amount: 10-48 As/dm 2
• the roughening plating treatment can be performed in multiple stages under the plating treatment condition 1 and/or the plating treatment condition 2.
• each treatment film contains an alloy containing copper, cobalt, and nickel, and the mass ratio of nickel in each treatment film is 1, the mass ratio of cobalt in each treatment film is 1.50 to 4.50. is preferred.
• the lower limit of the mass ratio of cobalt is, for example, 1.50, or, for example, 1.80, or, for example, 1.90.
• the mass ratio of cobalt is, for example, 4.50 or 4.20 as the upper limit.
• the mass ratio in the treated film containing the alloy containing copper, cobalt and nickel described above can be obtained based on the following formula (1).
• the mass ratio of nickel in each treated film is set to 1
• the mass ratio of cobalt in each treated film [coated amount of Co on treated film ( ⁇ g/dm 2 )/amount of Ni deposited on treated film ( ⁇ g/dm 2 ) ] (1)
• At least one of the following heat-resistant films 1 to 8 can be formed on the electromagnetic wave absorption auxiliary film described above.
• Each plating condition and vapor deposition condition are shown below.
• a nickel-chromium alloy deposition film is formed using a sputtering target having a composition of 65 to 85 mass% nickel and 15 to 35 mass% chromium.
• Target Nickel 65-85 mass%, Chromium 15-35 mass%
• Device Sputtering device manufactured by ULVAC, Inc.
• Output DC50W Argon pressure: 0.2 Pa
• the following rust prevention film and/or weather resistant film can be further formed on the electromagnetic wave absorption auxiliary film or heat resistant film described above. Each condition is shown below.
• Liquid composition 1 to 10 g/L potassium dichromate, 0.2 to 0.5 g/L zinc pH: 3-4
• Liquid temperature 50-70°C
• Current density 0 to 2 A/dm 2 (0 A/dm 2 is for immersion chromate treatment)
• Coulomb amount 0 to 2 As/dm 2 (0 As/dm 2 is for immersion chromate treatment)
• Types of weather resistant film (silane coupling film)
• One example is application of a diaminosilane aqueous solution or an epoxysilane aqueous solution.
• a metal film such as a heat-resistant film or a plated film is provided by vapor deposition such as sputtering, or when a metal film such as a heat-resistant film or a plated film is provided by plating, the heat-resistant film etc.
• the metal film and plating film are normal plating (smooth plating, that is, plating performed at a current density less than the critical current density)
• the metal film and plating film do not affect the shape of the surface of the copper foil.
• the limiting current density varies depending on the metal concentration, pH, liquid supply speed, inter-electrode distance, and plating solution temperature.
• the limit current density is defined as the current density at the boundary between burnt plating and plated metal deposited in crystal form (spherical, needle-like, rime-like, etc.) and unevenness.
• the current density (visual judgment) at the limit of normal plating (immediately before burning plating) is defined as the limit current density.
• the metal concentration, pH, and plating solution temperature are set to the manufacturing conditions for plating, and the Hull cell test is performed. Then, the composition of the plating solution and the state of formation of the metal layer (whether the plated metal is deposited in layers or in the form of crystals) at the temperature of the plating solution is investigated.
• the current density at the position of the boundary between the normal plating and the roughened plating of the test piece is determined from the position of the test piece. Then, the current density at the boundary position is defined as the limit current density. From this, the composition of the plating solution and the limit current density at the temperature of the plating solution can be obtained. In general, when the inter-electrode distance is short, the critical current density tends to be high.
• the Hull cell test method is described, for example, in "Plating Practical Reading Book” by Kiyoshi Maruyama, Nikkan Kogyo Shimbun, June 30, 1983, pp. 157-160.
• the current density during plating is preferably 20 A/dm 2 or less, more preferably 10 A/dm 2 or less, and 8 A/dm 2 or less . It is more preferable to:
• the antirust film and the weather resistant film are extremely thin, they do not affect the shape of the surface of the copper foil.
• each electromagnetic wave absorption assisting film is generally 0.001 ⁇ m to 0.8 ⁇ m, and other heat-resistant films each have a thickness of nanometers. Thickness and can.
• the average thickness (L2) of each non-magnetic conductive metal layer is not particularly limited and can be set as appropriate, and is, for example, within the range of 1.2 ⁇ m to 150 ⁇ m.
• the lower limit of the average thickness (L2) is, for example, 5.0 ⁇ m or more, or, for example, 12 ⁇ m or more.
• the average thickness (L2) is, for example, 75 ⁇ m or less, or 50 ⁇ m or less, as an upper limit.
• the average thickness (L3) of each ferromagnetic layer is not particularly limited and can be set as appropriate, but is, for example, within the range of 10 ⁇ m to 120 ⁇ m.
• the lower limit of the average thickness (L3) is, for example, 20 ⁇ m or more, or, for example, 30 ⁇ m or more.
• the average thickness (L3) is, for example, 100 ⁇ m or less, or, for example, 60 ⁇ m or less as an upper limit side.
• L1 can be obtained with an STEM image using a transmission electron microscope, and the thicknesses of L2 and L3 can be measured using a thickness gauge.
• the number of non-magnetic conductive metal layers in the electromagnetic wave shielding material should be 5 or less, and the number of ferromagnetic layers should be 4 or less.
• an adhesive may be used between the ferromagnetic layer and the non-magnetic conductive metal layer, or the ferromagnetic layer may be laminated to the non-magnetic conductive metal layer without using an adhesive.
• a simple stacking method without using an adhesive may be used, but considering the integrity of the electromagnetic wave shielding material, at least the ends (for example, each side if the shielding material is a square) are bonded with tape, adhesive, or by thermocompression bonding. preferably. However, from the viewpoint of not applying excessive heat to the ferromagnetic layer, it is preferable to use an adhesive.
• the adhesive is the same as described above and is not particularly limited, but acrylic resin, epoxy resin, urethane, polyester, silicone resin, vinyl acetate, styrene-butadiene rubber, nitrile rubber, phenol Resin-based, cyanoacrylate-based, and the like can be mentioned, and urethane-based, polyester-based, and vinyl acetate-based are preferred for the reasons of ease of production and cost.
• the thickness of the adhesive layer is preferably 100 ⁇ m or less. If the thickness of the adhesive layer exceeds 100 ⁇ m, the stress on the non-magnetic conductive metal layer and ferromagnetic layer, which are the layers to be adhered, increases when the adhesive layer is bent, and the layer is likely to break.
• the thickness is not limited to this, and the thickness can be set as described in the description of the ferromagnetic layer.
• it can have a magnetic field shielding characteristic (how much the signal is attenuated at the receiving end) of 15 dB or more at 100 kHz, preferably 18 dB or more, more preferably It can have a magnetic field shielding characteristic of 20 dB or more, more preferably 24 dB or more, and still more preferably 30 dB or more.
• magnetic field shielding characteristics are measured by the KEC method.
• the KEC method refers to the "Electromagnetic wave shielding characteristic measurement method" established by the Kansai Electronics Industry Promotion Center.
• coating materials for electrical and electronic devices e.g., inverters, communication devices, resonators, electron tubes/discharge lamps, electrical heating devices, motors, generators, electronic components, printed circuits, medical devices, etc.
• electrical and electronic devices e.g., inverters, communication devices, resonators, electron tubes/discharge lamps, electrical heating devices, motors, generators, electronic components, printed circuits, medical devices, etc.
• electromagnetic wave shielding applications such as exterior materials, harnesses connected to electrical and electronic equipment, covering materials for communication cables, electromagnetic wave shielding sheets, electromagnetic wave shielding panels, electromagnetic wave shielding bags, electromagnetic wave shielding boxes, and electromagnetic wave shielding rooms. is.
• magnetic layer means a ferromagnetic layer
• conductive layer means a non-magnetic conductive metal layer
• a Cu—Co—Ni alloy plating was formed on the rolled copper foil TPC under the conditions shown below.
• electromagnetic wave absorption assisting films made of particle films of copper, cobalt and nickel were formed on both surfaces of the rolled copper foil TPC.
• a heat-resistant film (plated film) made of cobalt and nickel by heat-resistant plating a heat-resistant film (plated film) made of nickel and zinc by heat-resistant plating, a rust-proof film (plated film) made of chromic acid by rust-proofing, and a weather-resistant film (coating film) was formed by silane coupling treatment.
• Example 1-2 on one surface (upper surface) of the rolled copper foil TPC, an electromagnetic wave absorption assisting film (plating film) made of a particle film of copper, cobalt and nickel, and made of cobalt and nickel by plating.
• An electromagnetic wave absorption assisting film made of a particle film of copper, cobalt and nickel, and made of cobalt and nickel by plating.
• Heat-resistant film made of nickel and zinc by plating
• anti-rust film plated film made of chromic acid by anti-rust treatment
• weather-resistant film coated film by silane coupling treatment membrane
• a heat-resistant film (plating film) made of nickel and zinc is plated without applying an electromagnetic wave absorption auxiliary film (plating film), and a chromium film is applied by rust prevention treatment.
• a rust-preventing film (plating film) made of acid was formed. It should be noted that the total thickness of the electromagnetic wave shielding material in the table is not shown including the thickness of the treated film because it is assumed that the film thickness of the treated film of the heat-resistant film and the antirust film is less than 0.1 ⁇ m.
• the bath compositions and plating conditions used to form the electromagnetic wave absorption assisting film, the heat-resistant plating film, the rust-proof film, and the weather-resistant film are as follows.
• Example 1-2 in order to form a treated film on one surface of the rolled copper foil TPC, the following (A) to (D) current densities and coulomb amounts were appropriately adjusted for the upper surface conditions.
• Electromagnetic wave absorption auxiliary film (Cu—Co—Ni alloy plating treatment (roughening plating treatment)) Liquid composition: copper 15.5 g/L, cobalt 7.0 g/L, nickel 9.3 g/L pH: 2.3 Liquid temperature: 36.0°C Current density : (Upper surface) 1st time: 21.3 A/dm 2 , 2nd time: 29.9 A/dm 2 , 3rd time: 56.8 A/dm 2 (Lower surface) 1st time: 14.9 A/dm 2 , 2nd time: 26.1 A/dm 2 , 3rd time: 56.8 dm 2 Coulomb quantity: (Upper surface) 1st time: 15.3 As/dm 2 , 2nd time: 21.5 As/dm 2 , 3rd time: 20.5 As/dm 2 (Lower surface) 1st time: 10.7 As/dm 2 , 2nd time: 18.8
• Example 6 a Cu—Ni alloy plating was formed on the electrolytic copper foil under the conditions shown below.
• an electromagnetic wave absorption auxiliary film (plated film) made of a copper and nickel particle film was formed as a treated film on one surface of the electrolytic copper foil.
• the table assumes that the film thickness of the treated film is 0.5 ⁇ m.
• the bath composition and plating conditions used to form the electromagnetic wave absorption auxiliary film are as follows. The following conditions were appropriately adjusted according to (F) below. The upper surface of the rolled copper foil flowing through the conveying plating line is defined as the upper surface.
• Electromagnetic wave absorption auxiliary film (Cu—Ni alloy plating treatment (roughening plating treatment)) Liquid composition: 15.5 g/L of copper, 9.5 g/L of nickel pH: 2.4 Liquid temperature: 36°C Current density : (Upper surface) 1st time: 44.7 A/dm 2 , 2nd time: 44.2 A/dm 2 , 3rd time: 63.2 A/dm 2 , 4th time: 63.2 A/dm 2 Coulomb quantity: (Upper surface) 1st time: 17.4 As/dm 2 , 2nd time: 20.2 As/dm 2 , 3rd time: 19.3 As/dm 2 , 4th time: 19.3 As/dm 2
• a smooth Ni plating film was formed on one surface of the electrolytic copper foil under the following conditions. Further, a rust preventive film was formed thereon under the conditions shown below.
• a smooth Ni plating film was formed on both surfaces of the electrolytic copper foil STD under the following conditions. Further, a rust preventive film was formed thereon under the conditions shown below.
• the bath composition and plating conditions used are as follows. The following conditions were appropriately adjusted according to the order of (H) to (I) below. In addition, the thickness of the treatment film composed of the smooth Ni film and the antirust film is assumed to be 0.5 ⁇ m in the table.
• Example 1-1 permalloy foil and rolled copper foil TPC having treated films containing copper, cobalt and nickel alloy plating formed on both surfaces were alternately laminated. An electromagnetic wave shielding material was obtained.
• Example 1-2 according to the configuration shown in Table 1, a permalloy foil and a treatment film containing copper, cobalt and nickel alloy plating were formed on one surface, and a heat-resistant film and rust prevention film were formed on the other surface.
• Example 6 according to the configuration shown in Table 1, a permalloy foil and an electrolytic copper foil having a treated film containing copper and nickel alloy plating formed on one surface were prepared, and the permalloy foil was divided into two sheets. An electromagnetic wave shielding material was obtained in which the permalloy foil and the electrolytic copper foil were alternately laminated so as to be sandwiched between the treated films of the electrolytic copper foil. In Reference Example 2, according to the configuration shown in Table 1, an electromagnetic wave shielding material was obtained in which treated films containing copper, cobalt and nickel alloy plating were formed on both surfaces of the rolled copper foil TPC.
• ⁇ Evaluation method> (Shielding evaluation) By fixing the upper and lower four corners of the KEC jig so that the rolled copper foil TPC or electrolytic copper foil and the permalloy foil or nickel foil constituting the electromagnetic wave shielding material do not shift during measurement, the electromagnetic wave The shielding material was placed in a magnetic field shielding property evaluation device (Techno Science Japan, Model TSES-KEC). Then, the electromagnetic wave shielding materials obtained in Examples 1-1 to 6, Comparative Examples 1 to 8, and Reference Examples 1 and 2 were subjected to frequency A magnetic field shielding characteristic for 100 kHz was evaluated. Table 1 shows the results.
• the electromagnetic wave shielding material is placed in a constant temperature and humidity chamber under conditions of temperature 85°C and humidity 85% Rh, and weather resistance is determined by checking the discoloration state of the surface of the electromagnetic wave shielding material after 200 hours (after standing still). evaluated. If no discoloration was observed on the surface of the electromagnetic wave shielding material before and after standing still in the device, it was judged as " ⁇ ", while electromagnetic waves before and after standing still in the device. If discoloration was observed on the surface of the shielding material, it was judged as "x" and the results are shown in Table 1.
• a rolled copper foil obtained by forming a treated film obtained under the same conditions as in Examples 1-1 to 1-5 and Reference Example 2 on a rolled copper foil TPC was used as a sample.
• the film on the copper foil surface of 50 mm ⁇ 50 mm was dissolved in an HNO 3 (30% by volume) aqueous solution, and the metal concentration in the 10-fold diluted aqueous solution was measured. was quantified using an ICP emission spectrometer (SFC-3100, manufactured by SII Nanotechnology Co., Ltd.), and the amount of metal per unit area ( ⁇ g/dm 2 ) was calculated and derived.
• the analysis was carried out after masking as necessary so that the metal adhesion amount on the surface to be measured and the opposite surface would not be mixed.
• the mass ratio of nickel in each treated film was 1
• the mass ratio of cobalt in each treated film was 2.3 on the upper surface side of the rolled copper foil and 2.1 on the lower surface side.
• Examples 1-1 to 1-6 compared with the corresponding Comparative Examples 1 to 6, by having a treated film containing an alloy containing copper and nickel on at least one surface of the non-magnetic conductive metal layer, low The shielding characteristics in the frequency domain were good, and Examples 1-1 to 1-6 had ferromagnetic layers compared to Reference Example 2. From these points, it has a ferromagnetic layer and a non-magnetic conductive metal layer, and further has a treated film containing an alloy containing copper and nickel on at least one surface of the non-magnetic conductive metal layer. It can be seen that an electromagnetic wave shielding material exhibiting good shielding properties was obtained.
• the outermost layer of at least one of the electromagnetic wave shielding materials is a non-magnetic conductive metal layer, and the antirust film is included in the treated film formed on the outer surface of the non-magnetic conductive metal layer. Or, by having a weather resistant film, the weather resistance was good.

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• 2022
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