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WO2015182377A1 - Film faiblement magnétique - Google Patents

Film faiblement magnétique Download PDF

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Publication number
WO2015182377A1
WO2015182377A1 PCT/JP2015/063645 JP2015063645W WO2015182377A1 WO 2015182377 A1 WO2015182377 A1 WO 2015182377A1 JP 2015063645 W JP2015063645 W JP 2015063645W WO 2015182377 A1 WO2015182377 A1 WO 2015182377A1
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Prior art keywords
soft magnetic
resin
less
magnetic film
volume
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PCT/JP2015/063645
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English (en)
Japanese (ja)
Inventor
菜穂 鎌倉
亮人 松富
剛志 土生
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Nitto Denko Corp
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Nitto Denko Corp
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets

Definitions

  • the present invention relates to a soft magnetic film.
  • a position detection device that detects a position by moving a pen-type position indicator on a position detection plane is called a digitizer and is widely used as an input device for a computer.
  • This position detection device includes a position detection flat plate, and a circuit board (sensor board) disposed under the position detection flat board and having a loop coil formed on the surface of the board. And the position of a position indicator is detected by utilizing the electromagnetic induction which a position indicator and a loop coil generate
  • the position detection device is provided with a soft magnetic film containing a soft magnetic material on the surface opposite to the position detection plane of the sensor substrate in order to control the magnetic flux generated during electromagnetic induction and improve communication efficiency.
  • a method of arranging has been proposed (see, for example, Patent Document 1).
  • Patent Document 1 discloses a soft magnetic film containing soft magnetic powder, a binder resin composed of acrylic rubber, phenol resin, epoxy resin, melamine, and the like, and a phosphinic acid metal salt.
  • This soft magnetic film contains flame retardant to the circuit board without affecting the reliability of the electronic device by containing a large amount of phosphinic acid metal salt and melamine.
  • soft magnetic films contain soft magnetic particles in a high ratio in order to improve magnetic properties such as magnetic permeability.
  • the soft magnetic film is subjected to a high temperature treatment such as a reflow treatment after being mounted on the circuit board.
  • a high temperature treatment such as a reflow treatment
  • the voids in the soft magnetic film expand due to the reflow process.
  • the soft magnetic film is peeled off or the appearance is poor.
  • the magnetic powder contains only about 45% by volume of the entire magnetic film (see paragraph [0067] of Patent Document 1).
  • An object of the present invention is to provide a soft magnetic film containing soft magnetic particles at a high ratio and having excellent reflow resistance.
  • the present invention [1] A soft magnetic film formed from a soft magnetic resin composition, wherein the soft magnetic resin composition contains flat soft magnetic particles and a resin component, and the soft magnetic film has a soft magnetic film composition.
  • soft magnetic particles are contained in a high ratio, and the reflow resistance is excellent.
  • FIG. 1 shows a cross-sectional view of a soft magnetic multilayer circuit board provided with an embodiment of the soft magnetic film of the present invention.
  • the soft magnetic film of the present invention is formed into a film shape (sheet shape) from, for example, a soft magnetic resin composition containing soft magnetic particles and a resin component.
  • the soft magnetic material constituting the soft magnetic particles examples include magnetic stainless steel (Fe—Cr—Al—Si alloy), sendust (Fe—Si—A1 alloy), permalloy (Fe—Ni alloy), silicon copper (Fe— Cu-Si alloy), Fe-Si alloy, Fe-Si-B (-Cu-Nb) alloy, Fe-Si-Cr-Ni alloy, Fe-Si-Cr alloy, Fe-Si-Al-Ni-Cr alloy And ferrite.
  • Sendust Fe—Si—Al alloy
  • the soft magnetic particles are formed in a flat shape (plate shape), that is, in a shape having a small thickness and a wide surface.
  • the flatness (flatness) of the soft magnetic particles is, for example, 8 or more, preferably 15 or more, and for example, 80 or less, preferably 65 or less.
  • the flatness is calculated, for example, as an aspect ratio obtained by dividing the average particle diameter (average length) of the soft magnetic particles by the average thickness of the soft magnetic particles.
  • the average particle diameter (average length) of the soft magnetic particles is, for example, 3.5 ⁇ m or more, preferably 10 ⁇ m or more, and for example, 100 ⁇ m or less, preferably 80 ⁇ m or less.
  • the average thickness is, for example, 0.3 ⁇ m or more, preferably 0.5 ⁇ m or more, and for example, 3 ⁇ m or less, preferably 2.5 ⁇ m or less.
  • the specific gravity of the soft magnetic particles is, for example, 5.0 or more and 8.0 or less.
  • the volume ratio of the soft magnetic particles in the soft magnetic resin composition is, for example, 65% by volume or more, preferably 70% by volume or more, for example, 95% by volume or less, preferably 90% by volume or less in terms of solid content. It is.
  • the mass ratio is, for example, in excess of 85% by mass, preferably 88% by mass or more, more preferably 90% by mass or more, and for example, 98% by mass or less, preferably in terms of solid content. 95 mass% or less.
  • the volume ratio of each component such as soft magnetic particles is calculated based on the theoretical volume obtained by dividing the mass of each component by the specific gravity of the component.
  • the specific gravity of each component is obtained by a catalog value or a known measurement method (for example, a specific gravity measurement method described later).
  • the resin component preferably contains a thermosetting resin and an acrylic resin. More preferably, the thermosetting resin which consists of an epoxy resin and a phenol resin, and an acrylic resin are contained.
  • the epoxy resin preferably includes an epoxy resin (polyfunctional monomer type epoxy resin) composed of a polyfunctional monomer having two or more functional groups (such as a glycidyl group) as a repeating unit.
  • an epoxy resin polyfunctional monomer type epoxy resin
  • a polyfunctional monomer having two or more functional groups such as a glycidyl group
  • the polyfunctional monomer type epoxy is preferably a trishydroxyphenylmethane type epoxy resin, a tetraphenylolethane type epoxy resin, or the like.
  • a trishydroxyphenylmethane type epoxy resin is used.
  • Specific examples include trishydroxyphenylmethane type epoxy resin represented by the following general formula (1).
  • n the degree of polymerization of the monomer.
  • thermosetting resin By containing a polyfunctional monomer type epoxy resin as the thermosetting resin, the melting temperature can be lowered, and it can be crosslinked and cured closely with the phenol resin described later. Therefore, when a soft magnetic resin composition containing a high content of soft magnetic particles (for example, 65% by volume or more) is compressed to produce a soft magnetic film with a high filling rate, due to the repulsive force between the soft magnetic particles. Generation of cracks in the resin composition and thus generation of voids (spring back) can be suppressed, and a soft magnetic film having a lower porosity can be produced more reliably.
  • a soft magnetic resin composition containing a high content of soft magnetic particles for example, 65% by volume or more
  • the epoxy equivalent of the epoxy resin is, for example, 10 g / eq. Or more, preferably 100 g / eq. In addition, for example, 500 g / eq. Hereinafter, preferably, 180 g / eq. It is as follows.
  • the viscosity (150 ° C.) of the epoxy resin is, for example, 1.0 Pa ⁇ s or less, preferably 0.2 Pa ⁇ s or less, and 0.01 Pa ⁇ s or more. Viscosity is measured with an ICI viscometer.
  • the specific gravity of the epoxy resin is, for example, 1.0 or more and 1.5 or less.
  • the phenol resin is a thermosetting resin that serves as a curing agent for the epoxy resin, and examples thereof include a phenol novolak resin, a cresol novolac resin, a phenol aralkyl resin, a phenol biphenylene resin, a dicyclopentadiene type phenol resin, and a resole resin. These can be used alone or in combination of two or more.
  • a phenol novolac resin is preferable.
  • a phenol novolac resin that can shorten the cross-linking point distance for a polyfunctional monomer type epoxy resin having a plurality of functional groups in the repeating unit, the polyfunctional monomer type epoxy resin and the phenol novolac resin It is possible to crosslink densely and obtain a cured resin with higher strength. For this reason, the spring back of soft magnetic particles can be reliably suppressed, and a soft magnetic film having a particularly low porosity can be obtained.
  • the hydroxyl equivalent of the phenol resin is, for example, 10 g / eq. Or more, preferably 80 g / eq. In addition, for example, 500 g / eq. Hereinafter, preferably, 150 g / eq. It is as follows.
  • the viscosity (150 ° C.) of the phenol resin is, for example, 0.10 Pa ⁇ s or less, preferably 0.04 Pa ⁇ s or less, and 0.01 Pa ⁇ s or more.
  • the specific gravity of the phenol resin is, for example, 1.0 or more and 1.5 or less.
  • an acrylic resin for example, an acrylic polymer obtained by polymerizing one or two or more (meth) acrylic acid alkyl esters having a linear or branched alkyl group as a monomer component, and the like are polymerized.
  • (meth) acryl means “acryl and / or methacryl”.
  • alkyl group examples include methyl, ethyl, propyl, isopropyl, n-butyl, t-butyl, isobutyl, amyl, isoamyl, hexyl, heptyl, cyclohexyl, 2- Alkyl having 1 to 20 carbon atoms such as ethylhexyl group, octyl group, isooctyl group, nonyl group, isononyl group, decyl group, isodecyl group, undecyl group, lauryl group, tridecyl group, tetradecyl group, stearyl group, octadecyl group, dodecyl group Groups.
  • an alkyl group having 1 to 6 carbon atoms is used.
  • the acrylic polymer may be a copolymer of (meth) acrylic acid alkyl ester and other monomers.
  • Examples of other monomers include glycidyl group-containing monomers such as glycidyl acrylate and glycidyl methacrylate, such as acrylic acid, methacrylic acid, carboxyethyl acrylate, carboxypentyl acrylate, itaconic acid, maleic acid, fumaric acid, and crotonic acid.
  • glycidyl group-containing monomers such as glycidyl acrylate and glycidyl methacrylate, such as acrylic acid, methacrylic acid, carboxyethyl acrylate, carboxypentyl acrylate, itaconic acid, maleic acid, fumaric acid, and crotonic acid.
  • acid anhydride monomers such as maleic anhydride, itaconic anhydride, such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, 12-hydroxylauryl (meth) acrylate or (4-hydride) Hydroxyl group-containing monomers such as xymethylcyclohexyl) -methyl acrylate, such as styrene sulfonic acid, allyl sulfonic acid, 2- (meth) acrylamide-2-methylpropane sulfonic acid, (meth) acrylamide propane sulfonic acid, sulfopropyl (meta ) Acrylate, sulfonic acid group-containing monomer such as (
  • the acrylic resin preferably has an epoxy group.
  • the epoxy value is, for example, 10 eq. / G or more, preferably 100 eq. / G or more, for example, 800 eq. / G or less, preferably 500 eq. / G or less.
  • the weight average molecular weight of the acrylic resin is, for example, 1 ⁇ 10 5 or more, preferably 3 ⁇ 10 5 or more, and for example, 1 ⁇ 10 6 or less.
  • a weight average molecular weight is measured by a standard polystyrene conversion value by gel permeation chromatography (GPC).
  • the glass transition temperature (Tg) of the acrylic resin is, for example, ⁇ 20 ° C. or higher, preferably 0 ° C. or higher, more preferably 10 ° C. or higher, and further preferably 12 ° C. or higher. For example, it is 50 degrees C or less, Preferably, it is 30 degrees C or less.
  • Tg of acrylic resin is more than the said minimum, the intensity
  • the soft magnetic film can be handled and the adhesive property of the soft magnetic thermosetting film in a semi-cured state is excellent.
  • the glass transition temperature is obtained from the maximum value of the loss tangent (tan ⁇ ) measured using a dynamic viscoelasticity measuring device (DMA, frequency 1 Hz, tensile mode, heating rate 10 ° C./min).
  • DMA dynamic viscoelasticity measuring device
  • the specific gravity of the acrylic resin is, for example, 0.6 or more and 1.0 or less.
  • the resin component can also contain other resins other than the thermosetting resin and the acrylic resin.
  • Such resins include natural rubber, butyl rubber, isoprene rubber, chloroprene rubber, ethylene-vinyl acetate copolymer, polybutadiene resin, polycarbonate resin, thermoplastic polyimide resin, polyamide resin (6-nylon, 6,6- Nylon), phenoxy resin, saturated polyester resin (PET, PBT, etc.), polyamideimide resin, fluororesin and the like. These can be used alone or in combination of two or more.
  • the volume ratio of the resin component in the soft magnetic resin composition is, for example, 5% by volume or more, preferably 10% by volume or more, and, for example, 35% by volume or less, preferably 30% by volume in terms of solid content. It is as follows.
  • the mass ratio of the resin component in the soft magnetic resin composition is, for example, 2% by mass or more, preferably 5% by mass or more, in terms of solid content, for example, less than 15% by mass, preferably 12% by mass. Hereinafter, it is more preferably 10% by mass or less.
  • the content ratio of the resin component is within the above range, the soft magnetic film is excellent in film formability and magnetic characteristics.
  • the volume ratio of the thermosetting resin (preferably a thermosetting resin composed of an epoxy resin and a phenol resin) in the resin component is, for example, 85% by volume or more, preferably 90% by volume or more, and more preferably 95% by volume. For example, it is 99% by volume or less, preferably 97% by volume or less.
  • the volume ratio of the epoxy resin in the resin component is, for example, 10% by volume or more, preferably 30% by volume or more, more preferably more than 50% by volume, and for example, 90% by volume or less, preferably 80% by volume. % Or less, more preferably 70% by volume or less.
  • the mass ratio of the epoxy resin in the resin component is, for example, 10% by mass or more, preferably 30% by mass or more, more preferably more than 50% by mass, and for example, 90% by mass or less, preferably 80% by mass. % Or less, more preferably 70% by mass or less.
  • the volume ratio of the phenol resin in the resin component is, for example, 10% by volume or more, preferably 20% by volume or more, more preferably more than 30% by volume, and for example, 90% by volume or less, preferably 70% by volume. % Or less, more preferably less than 50% by volume.
  • the mass ratio of the phenol resin in the resin component is, for example, 10% by mass or more, preferably 20% by mass or more, more preferably more than 30% by mass, and for example, 90% by mass or less, preferably 70% by mass. % Or less, more preferably less than 50% by mass.
  • the content rate of the phenol resin with respect to 100 volume parts of epoxy resins is 10 volume parts or more, Preferably, it is 50 volume parts or more, for example, is 200 volume parts or less, Preferably, it is less than 100 volume parts. .
  • the volume ratio of the acrylic resin in the resin component is, for example, 1% by volume or more, preferably 3% by volume or more, and for example, 25% by volume or less, preferably 15% by volume or less, more preferably 10% by volume. % Or less, more preferably 5% by volume or less.
  • the mass ratio of the acrylic resin in the resin component is, for example, 1% by mass or more, preferably 3% by mass or more, and for example, 25% by mass or less, preferably 15% by mass or less, more preferably 10% by mass. % Or less, more preferably 5% by mass or less.
  • the soft magnetic resin composition preferably contains a thermosetting catalyst.
  • thermosetting catalyst is not limited as long as it is a catalyst that promotes curing of the resin component by heating, and examples thereof include imidazole compounds, triphenylphosphine compounds, triphenylborane compounds, amino group-containing compounds, and the like. It is done. Preferably, an imidazole compound is used.
  • imidazole compounds examples include 2-phenylimidazole (trade name; 2PZ), 2-ethyl-4-methylimidazole (trade name; 2E4MZ), 2-methylimidazole (trade name; 2MZ), and 2-undecylimidazole.
  • (Trade name; C11Z) 2-phenyl-1H-imidazole 4,5-dimethanol (trade name; 2PHZ-PW), 2,4-diamino-6- (2′-methylimidazolyl (1) ′) ethyl-
  • Examples include s-triazine / isocyanuric acid adduct (trade name: 2MAOK-PW) (all trade names are manufactured by Shikoku Kasei Co., Ltd.). These can be used alone or in combination of two or more.
  • the specific gravity of the thermosetting catalyst is, for example, 0.9 or more and 1.5 or less.
  • the content ratio of the thermosetting catalyst is, for example, 0.1 part by volume or more, preferably 0.3 part by volume or more, and for example, 5 parts by volume or less, preferably 100 parts by volume of the resin component. 3 parts by volume or less.
  • the mass ratio of the thermosetting catalyst is, for example, 0.1 parts by mass or more, preferably 0.3 parts by mass or more, and for example, 5 parts by mass or less, preferably 100 parts by mass of the resin component. 3 parts by mass or less.
  • the soft magnetic resin composition can also contain a rheology control agent.
  • the soft magnetic particles can be more uniformly dispersed in the soft magnetic film.
  • a rheology control agent is a compound that imparts a thixotropic property to a soft magnetic resin composition that exhibits high viscosity when the shearing force (shear rate) is low and low viscosity when the shearing force (shear rate) is high. is there.
  • rheology control agent examples include organic rheology control agents and inorganic rheology control agents.
  • organic rheology control agent is used.
  • organic rheology control agent examples include modified urea, urea-modified polyamide, fatty acid amide, polyurethane, and polymer urea derivative.
  • Preferred examples include modified urea, urea-modified polyamide, and fatty acid amide, and more preferable examples include urea-modified polyamide.
  • Examples of the inorganic rheology control agent include silica, calcium carbonate, smectite and the like.
  • rheology control agent examples include, for example, “BYK-410”, “BYK-430”, “BYK-431” manufactured by BYK Chemie, for example, “Disparon PFA-131” manufactured by Enomoto Kasei Co., Ltd. Aerosil's “Aerosil VP NK200”, “Aerosil R976S”, “Aerosil COK84” and the like.
  • the specific gravity of the rheology control agent is, for example, 0.6 or more and 1.0 or less.
  • the volume ratio of the rheology control agent is, for example, 0.1 part by volume or more, preferably 1 part by volume or more, and for example, 10 parts by volume or less, preferably 5 volumes with respect to 100 parts by volume of the resin component. Or less.
  • the mass ratio of the rheology control agent is, for example, 0.1 parts by mass or more, preferably 1 part by mass or more, and for example, 10 parts by mass or less, preferably 5 parts by mass with respect to 100 parts by mass of the resin component. Or less.
  • the soft magnetic resin composition may further contain other additives as necessary.
  • additives commercially available or well-known things, such as a dispersing agent, a crosslinking agent, an inorganic filler, are mentioned, for example.
  • the tensile storage elastic modulus E ′ at 160 ° C. at a heating rate of 10 ° C./min and a frequency of 1 Hz in the dynamic viscoelasticity measurement of the soft magnetic particle excluded component excluding the soft magnetic particles from the soft magnetic resin composition is, for example, 5 0.5 ⁇ 10 8 Pa or more, preferably 8.0 ⁇ 10 8 Pa or more, for example, 3.0 ⁇ 10 9 Pa or less, preferably 1.0 ⁇ 10 9 Pa or less.
  • the tensile storage elastic modulus E ′ of the soft magnetic particle exclusion component is within the above range, the porosity of the soft magnetic film can be further reduced.
  • the tensile storage elastic modulus E ′ will be described in detail in Examples.
  • the soft magnetic resin composition is prepared by mixing the above components in the above content ratio.
  • the soft magnetic film is prepared by, for example, preparing or preparing a soft magnetic resin composition solution by dissolving or dispersing the soft magnetic resin composition in a solvent. It can be manufactured by a drying process for obtaining a cured soft magnetic thermosetting film and a hot pressing process in which a plurality of soft magnetic thermosetting films are stacked and hot pressed.
  • the soft magnetic resin composition is dissolved or dispersed in a solvent (preparation step). Thereby, a soft magnetic resin composition solution is prepared.
  • the solvent examples include ketones such as acetone and methyl ethyl ketone (MEK), esters such as ethyl acetate, ethers such as propylene glycol monomethyl ether, amides such as N, N-dimethylformamide, and the like.
  • MEK methyl ethyl ketone
  • esters such as ethyl acetate
  • ethers such as propylene glycol monomethyl ether
  • amides such as N, N-dimethylformamide, and the like.
  • An organic solvent etc. are mentioned.
  • the solvent also include aqueous solvents such as water, for example, alcohols such as methanol, ethanol, propanol, and isopropanol.
  • the solid content in the soft magnetic resin composition solution is, for example, 10% by mass or more, preferably 30% by mass or more, and for example, 90% by mass or less, preferably 70% by mass or less.
  • the soft magnetic resin composition solution is applied to the surface of a release substrate (separator, core material, etc.) and dried (drying step).
  • Application method is not particularly limited, and examples thereof include a doctor blade method, roll coating, screen coating, and gravure coating.
  • the drying temperature is, for example, 70 ° C. or more and 160 ° C. or less
  • the drying time is, for example, 1 minute or more and 5 minutes or less.
  • separator examples include a polyethylene terephthalate (PET) film, a polyethylene film, a polypropylene film, and paper. These are subjected to mold release treatment on the surface with, for example, a fluorine release agent, a long-chain alkyl acrylate release agent, a silicone release agent, or the like.
  • PET polyethylene terephthalate
  • a fluorine release agent for example, a fluorine release agent, a long-chain alkyl acrylate release agent, a silicone release agent, or the like.
  • the core material examples include plastic films (eg, polyimide film, polyester film, polyethylene terephthalate film, polyethylene naphthalate film, polycarbonate film, etc.), metal films (eg, aluminum foil, etc.), such as glass fiber and plastic Examples include resin substrates reinforced with woven fibers, silicone substrates, glass substrates, and the like.
  • plastic films eg, polyimide film, polyester film, polyethylene terephthalate film, polyethylene naphthalate film, polycarbonate film, etc.
  • metal films eg, aluminum foil, etc.
  • glass fiber and plastic examples include resin substrates reinforced with woven fibers, silicone substrates, glass substrates, and the like.
  • the average thickness of the separator or core material is, for example, 1 ⁇ m or more and 500 ⁇ m or less.
  • the average thickness of the soft magnetic thermosetting film is, for example, 5 ⁇ m or more, preferably 50 ⁇ m or more, and for example, 500 ⁇ m or less, preferably 250 ⁇ m or less.
  • the soft magnetic thermosetting films are prepared, and the plurality of soft magnetic thermosetting films are hot-pressed in the thickness direction by hot pressing (hot pressing step).
  • the semi-cured soft magnetic thermosetting film is cured by heating.
  • the soft magnetic film can be filled with soft magnetic particles at a high ratio to improve the magnetic properties.
  • the hot press can be performed using a known press machine, for example, a parallel plate press machine.
  • the number of laminated soft magnetic thermosetting films is, for example, 2 layers or more, and for example, 20 layers or less, preferably 5 layers or less. Thereby, it can adjust to the soft-magnetic film of desired thickness.
  • the heating temperature is, for example, 80 ° C. or more, preferably 100 ° C. or more, and for example, 200 ° C. or less, preferably 180 ° C. or less.
  • the heating time is, for example, 0.1 hour or more, preferably 0.2 hours or more, and for example, 24 hours or less, preferably 2 hours or less.
  • the pressure is, for example, 10 MPa or more, preferably 20 MPa or more, and for example, 500 MPa or less, preferably 200 MPa or less.
  • the soft magnetic thermosetting film is cured by heating to obtain a soft magnetic film in a cured state (C stage state).
  • the average thickness of the soft magnetic film is, for example, 5 ⁇ m or more, preferably 50 ⁇ m or more, and for example, 500 ⁇ m or less, preferably 250 ⁇ m or less.
  • the porosity of the soft magnetic film is less than 2.5% by volume. Preferably, it is less than 2.0 volume%, More preferably, it is less than 1.0 volume%. Thereby, the reflow resistance of the soft magnetic film is excellent.
  • the porosity is measured by the following formula.
  • Porosity (%) ⁇ 1 ⁇ (specific gravity (SG)) / (theoretical specific gravity) ⁇ ⁇ 100
  • the specific gravity (SG) was determined by measuring the weight W1 (g) of the soft magnetic film in air and in water using an electronic analytical balance (manufactured by Shimadzu Corporation, “AEL-200”).
  • the weight (g) of the soft magnetic film W2 is measured and calculated by the following formula.
  • Specific gravity (SG) W1 / (W1-W2)
  • the theoretical specific gravity is, for example, a solid content component (soft magnetic particles, resin component, thermosetting catalyst, rheology control agent and other additives added as necessary) contained in the soft magnetic resin composition forming the soft magnetic film. Etc.) is obtained by multiplying the specific gravity of each solid component by the blending ratio (weight) of each solid component and adding them together.
  • the catalog value etc. can be referred for the specific gravity (for example, soft magnetic particle) of each solid content component.
  • the theoretical specific gravity of the soft magnetic film is that in the soft magnetic film consisting of only the soft magnetic particles and the resin component. The theoretical specific gravity can be substituted.
  • the theoretical specific gravity of the soft magnetic film is, for example, 2.0 or more, preferably 2.2 or more, and for example, 8.0 or less, preferably 6.0 or less.
  • the relative magnetic permeability ⁇ ′ of the soft magnetic film is, for example, 150 or more, preferably 180 or more, and for example, 500 or less.
  • the relative permeability ⁇ ′ is measured by a one-turn method (frequency 1 MHz) using an impedance analyzer (manufactured by Agilent, “4294A”).
  • the soft magnetic film preferably has flat soft magnetic particles contained in the soft magnetic film arranged in the two-dimensional in-plane direction of the soft magnetic film. That is, the flat soft magnetic particles are oriented so that the longitudinal direction (direction perpendicular to the thickness direction) is along the surface direction of the soft magnetic film. As a result, the soft magnetic film is filled with soft magnetic particles at a high ratio and has excellent magnetic properties. In addition, thinning of the soft magnetic film has been attempted.
  • This soft magnetic film has, for example, a single layer structure composed of only a single layer of a soft magnetic film, a multilayer structure in which a soft magnetic film is laminated on one or both sides of a core material, and a separator is laminated on one or both sides of a soft magnetic film.
  • a multi-layer structure can be used.
  • a plurality of soft magnetic thermosetting films are laminated and hot pressed.
  • one soft magnetic thermosetting film may be hot pressed. .
  • the soft magnetic resin contains flat soft magnetic particles and a resin component, and the volume ratio of the soft magnetic particles to the soft magnetic resin composition is 65% by volume or more in terms of solid content. Since the porosity of the soft magnetic film formed from the composition is 2.5% by volume or less, the soft magnetic film contains soft magnetic particles at a high filling rate (high density). Moreover, since the porosity of a soft magnetic film is 2.5 volume% or less, it is excellent in reflow resistance and the space
  • the soft magnetic film can suppress peeling and poor appearance of the soft magnetic film even after the reflow process. Also, good magnetic properties can be exhibited.
  • the soft magnetic film can be suitably used as, for example, an antenna, a coil, or a soft magnetic film for laminating on a circuit board on which these are formed.
  • the soft magnetic film includes a circuit board 2, an adhesive layer 3 disposed on a lower surface (one surface) of the circuit board 2, and a lower surface of the adhesive layer 3. It can be used as a soft magnetic film laminated substrate 1 provided with the soft magnetic film 4 arrange
  • the circuit board 2 is, for example, a circuit board 2 used in an electromagnetic induction system, and a wiring pattern 6 such as a loop coil is formed on the upper surface (one surface) of the substrate 5.
  • the wiring pattern 6 is formed by a semi-additive method or a subtractive method.
  • Examples of the insulating material constituting the substrate 5 include a glass epoxy substrate, a glass substrate, a PET substrate, a Teflon substrate, a ceramic substrate, and a polyimide substrate.
  • the adhesive layer 3 a known one that is usually used as an adhesive for the circuit board 2 is used.
  • an adhesive such as an epoxy adhesive, a polyimide adhesive, or an acrylic adhesive is applied and dried. It is formed by.
  • the thickness of the adhesive layer 3 is, for example, 10 to 100 ⁇ m.
  • the soft magnetic film 4 is the above-described soft magnetic film, and flat soft magnetic particles 7 are dispersed in a soft magnetic resin composition (specifically, a cured resin 8 in which a resin component is cured).
  • a soft magnetic resin composition specifically, a cured resin 8 in which a resin component is cured.
  • the soft magnetic particles 7 are oriented so that the longitudinal direction (the direction perpendicular to the thickness direction) is along the surface direction of the soft magnetic film 4.
  • Such a soft magnetic film laminated substrate 1 can be used for applications such as a smartphone, a personal computer, and a position detection device.
  • the adhesive layer 3 is provided between the circuit board 2 and the soft magnetic film 4.
  • the soft magnetic film 4 is in direct contact with the circuit board 2. It can also be provided.
  • a soft magnetic thermosetting film in a semi-cured state is directly attached to the circuit board 2, and then the soft magnetic thermosetting film is cured by heating.
  • the soft magnetic film laminated substrate 1 since the soft magnetic film 4 is provided, the space
  • the temperature in the reflow process is, for example, 200 ° C. or higher, preferably 250 ° C. or higher, and for example, 500 ° C. or lower, preferably 300 ° C. or lower.
  • the reflow storage time is, for example, 1 second or more, preferably 5 seconds or more, and for example, 10 minutes or less, preferably 5 minutes or less.
  • Example 1 500 parts by mass of Fe—Si—Al alloy (70.0% by volume, the following volume% is solid) so that the volume ratio of the soft magnetic particles to the soft magnetic resin composition is 70.0% by volume in terms of solid content. ), Trishydroxyphenylmethane type epoxy resin (EPPN-501HY) 21.9 parts by mass (17.0% by volume), phenol novolac resin (LVR8210DL) 13.5 parts by mass (10.4% by volume), 8.6 parts by mass (1.4% by volume) of an acrylic ester copolymer solution (SG-P3), 0.36 parts by mass (0.2% by volume) of an imidazole compound (thermosetting catalyst, 2PHZ-PW) A soft magnetic resin composition was obtained by mixing 3.0 parts by mass (1.0% by volume) of a urea-modified polyamide solution (rheology control agent, BYK430).
  • This soft magnetic resin composition was dissolved in methyl ethyl ketone to prepare a soft magnetic resin composition solution having a solid content concentration of 40% by mass.
  • This soft magnetic resin composition solution was applied onto a separator (polyethylene terephthalate film subjected to silicone release treatment) and then dried at 130 ° C. for 2 minutes. As a result, a semi-cured soft magnetic thermosetting film (average thickness 50 ⁇ m) was produced.
  • this soft magnetic thermosetting film is laminated and heated and cured by hot pressing under the conditions of 160 ° C., 30 minutes, 160 MPa, thereby producing a fully cured soft magnetic film (average thickness 150 ⁇ m). did.
  • Example 2 Soft magnetic resin compositions were obtained with the materials and blending ratios shown in Table 1. A soft magnetic film (average thickness 150 ⁇ m) of Example 2 was produced in the same manner as Example 1 except that the soft magnetic resin composition was used.
  • Comparative Examples 1 to 3 Soft magnetic resin compositions were obtained with the materials and blending ratios shown in Table 1.
  • a soft magnetic film of a comparative example was manufactured in the same manner as in Example 1 except that this soft magnetic resin composition was used.
  • Dynamic viscoelasticity measuring apparatus trade name “RSAIII”, manufactured by Rheometric Scientific Inc. Mode: Tensile mode Temperature rising rate: 10 ° C./min Frequency: 1 Hz Sample thickness: 40-130 ⁇ m Distance between chucks: 20mm Strain: 0.1% Measurement temperature range: 0 ° C to 200 ° C The results are shown in Table 1.
  • the specific gravity (SG) of the soft magnetic film of each Example and each Comparative Example was determined by measuring the specific gravity using an electronic analytical balance (“AEL-200” manufactured by Shimadzu Corporation) in the air.
  • AEL-200 manufactured by Shimadzu Corporation
  • the weight W1 (g) in the film and the weight (g) of the soft magnetic film W2 in water were measured and calculated by the following formula.
  • the soft magnetic films of each Example and each Comparative Example were laminated on one side of a circuit board via an acrylic adhesive to produce a soft magnetic film laminated board (see FIG. 1).
  • the soft magnetic film laminated substrate was passed through an IR reflow furnace under the condition of 260 ° C. for 10 seconds to carry out a reflow process.
  • the soft magnetic film laminated circuit board after this reflow process was visually observed.
  • the case where change was not confirmed in the external appearance of the soft magnetic film was evaluated as ⁇ , and the case where external appearance defects such as swelling and peeling were confirmed in the soft magnetic film was evaluated as ⁇ .
  • the results are shown in Table 1.
  • SG-P3 acrylate copolymer solution, trade name “Taisan Resin SG-P3”, containing epoxy group Ethyl acrylate-butyl acrylate-acrylonitrile copolymer, specific gravity 0.85, weight average molecular weight 850,000, epoxy value 210 eq.
  • the soft magnetic film of the present invention can be applied to various industrial products, and can be suitably used for, for example, smartphones, tablet computers, position detection devices, and the like.

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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Soft Magnetic Materials (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

　L'invention concerne un film faiblement magnétique formé à partir d'une composition de résine faiblement magnétique. La composition de résine faiblement magnétique contient des particules faiblement magnétiques plates et un composant de résine. Le rapport volumique des particules faiblement magnétiques par rapport à la composition de résine faiblement magnétique en termes de contenu solide est d'au moins 65 % en volume. La porosité du film faiblement magnétique est de 2,5 % en volume ou moins.
PCT/JP2015/063645 2014-05-29 2015-05-12 Film faiblement magnétique Ceased WO2015182377A1 (fr)

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WO2018105347A1 (fr) 2016-12-07 2018-06-14 日東電工株式会社 Procédé de production de module
WO2018105348A1 (fr) 2016-12-07 2018-06-14 日東電工株式会社 Procédé de fabrication de module
WO2018116127A1 (fr) * 2016-12-19 2018-06-28 3M Innovative Properties Company Composite polymère thermoplastique contenant un matériau particulaire ferromagnétique mou et ses procédés de fabrication
JP7105220B2 (ja) * 2019-12-26 2022-07-22 株式会社トーキン 複合磁性体シート及び複合磁性体シートの製造方法
CN115398569B (zh) * 2020-04-17 2025-08-15 富士胶片株式会社 磁性树脂组合物、固化物及电子零件
US11710588B2 (en) 2021-06-14 2023-07-25 Tokin Corporation Composite magnetic sheet and forming method of composite magnetic sheet

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WO2008053737A1 (fr) * 2006-10-31 2008-05-08 Sony Chemical & Information Device Corporation Matériau magnétique souple en forme de feuille et procédé de production de ce dernier
JP2009059752A (ja) * 2007-08-30 2009-03-19 Hitachi Chem Co Ltd 難燃化ノイズ抑制シート
WO2014132701A1 (fr) * 2013-02-26 2014-09-04 日東電工株式会社 Film magnétique doux adhésif thermodurcissable, circuit imprimé stratifié sur un film magnétique doux et détecteur de position

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JP6778991B2 (ja) * 2014-05-29 2020-11-04 日東電工株式会社 軟磁性熱硬化性フィルムおよび軟磁性フィルム
JP6812091B2 (ja) * 2014-05-29 2021-01-13 日東電工株式会社 軟磁性樹脂組成物および軟磁性フィルム

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Publication number Priority date Publication date Assignee Title
WO2008053737A1 (fr) * 2006-10-31 2008-05-08 Sony Chemical & Information Device Corporation Matériau magnétique souple en forme de feuille et procédé de production de ce dernier
JP2009059752A (ja) * 2007-08-30 2009-03-19 Hitachi Chem Co Ltd 難燃化ノイズ抑制シート
WO2014132701A1 (fr) * 2013-02-26 2014-09-04 日東電工株式会社 Film magnétique doux adhésif thermodurcissable, circuit imprimé stratifié sur un film magnétique doux et détecteur de position

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