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WO2015182377A1 - Soft-magnetic film - Google Patents

Soft-magnetic film 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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WO
WIPO (PCT)
Prior art keywords
soft magnetic
resin
less
magnetic film
volume
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PCT/JP2015/063645
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French (fr)
Japanese (ja)
Inventor
菜穂 鎌倉
亮人 松富
剛志 土生
Original Assignee
日東電工株式会社
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Publication of WO2015182377A1 publication Critical patent/WO2015182377A1/en

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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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Abstract

　This soft-magnetic film is formed from a soft-magnetic resin composition. The soft-magnetic resin composition contains flat soft-magnetic particles and a resin component. The volume ratio of the soft-magnetic particles with respect to the soft-magnetic resin composition in terms of solid content is at least 65 vol%. The porosity of the soft-magnetic film is 2.5 vol% or lower.

Description

軟磁性フィルムSoft magnetic film
　本発明は、軟磁性フィルムに関する。 The present invention relates to a soft magnetic film.
　ペン型の位置指示器を位置検出平面上で移動させて位置を検出する位置検出装置は、デジタイザと呼ばれ、コンピュータの入力装置として普及している。この位置検出装置は、位置検出平面板と、その下に配置され、ループコイルが基板の表面に形成された回路基板（センサ基板）とを備えている。そして、位置指示器とループコイルとによって発生する電磁誘導を利用することにより、位置指示器の位置を検出する。 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 | occur | produce.
　位置検出装置には、電磁誘導の際に発生する磁束を制御して通信を効率化するために、センサ基板の位置検出平面とは反対側の面に、軟磁性物質を含有する軟磁性フィルムを配置する方法が提案されている（例えば、特許文献１参照。）。 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).
　特許文献１には、軟磁性粉末と、アクリルゴム、フェノール樹脂、エポキシ樹脂およびメラミンなどからなるバインダ樹脂と、ホスフィン酸金属塩とを含有する軟磁性フィルムが開示されている。この軟磁性フィルムは、ホスフィン酸金属塩やメラミンが多くの割合で含有することによって、電子機器の信頼性に影響を与えず、回路基板に難燃性を付与している。 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.
特開２０１２－２１２７９０号公報JP 2012-212790 A
　しかるに、軟磁性フィルムでは、透磁率などの磁気特性の向上のため、軟磁性粒子を高い割合で含有させることが検討されている。 However, it has been studied that soft magnetic films contain soft magnetic particles in a high ratio in order to improve magnetic properties such as magnetic permeability.
　しかし、軟磁性粒子を高い割合で軟磁性フィルムに含有させると、軟磁性粒子同士の距離が接近するため、軟磁性粒子同士が反発する現象（スプリングバック）が生じる。その結果、軟磁性フィルムに、空隙（ボイド）や亀裂が生じる。 However, when soft magnetic particles are contained in a high ratio in the soft magnetic film, the distance between the soft magnetic particles approaches and a phenomenon (spring back) occurs in which the soft magnetic particles repel each other. As a result, voids and cracks are generated in the soft magnetic film.
　ところで、軟磁性フィルムは、回路基板に実装された後に、リフロー処理などの高温処理がなされる。しかし、軟磁性フィルムに空隙が多く存在すると、リフロー工程によって、軟磁性フィルム内の空隙が膨張する。その結果、軟磁性フィルムの剥離や外観不良が生じる不具合を生じる。 By the way, the soft magnetic film is subjected to a high temperature treatment such as a reflow treatment after being mounted on the circuit board. However, if there are many voids in the soft magnetic film, the voids in the soft magnetic film expand due to the reflow process. As a result, there arises a problem that the soft magnetic film is peeled off or the appearance is poor.
　したがって、例えば、特許文献１では、磁性粉末は、磁性フィルム全体の４５体積％程度しか含有されていない（特許文献１の［００６７］段落参照。）。 Therefore, for example, in Patent Document 1, the magnetic powder contains only about 45% by volume of the entire magnetic film (see paragraph [0067] of Patent Document 1).
　本発明の目的は、軟磁性粒子が高い割合で含有され、耐リフロー性に優れた軟磁性フィルムを提供することにある。 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.
　本発明は、
　［１］軟磁性樹脂組成物から形成される軟磁性フィルムであって、前記軟磁性樹脂組成物が、扁平状の軟磁性粒子および樹脂成分を含有し、前記軟磁性樹脂組成物に対する前記軟磁性粒子の体積割合が、固形分換算で、６５体積％以上であり、前記軟磁性フィルムの空隙率が、２．５体積％以下である軟磁性フィルム、
　［２］前記樹脂成分が、多官能モノマー型エポキシ樹脂、フェノール樹脂およびアクリル樹脂を含有し、前記樹脂成分に対する前記アクリル樹脂の体積割合が、１０体積％以下である［１］に記載の軟磁性フィルム、
　［３］前記アクリル樹脂のガラス転移温度が、０℃以上であることを特徴とする、［２］に記載の軟磁性フィルム、
　［４］前記軟磁性樹脂組成物から前記軟磁性粒子を除外した軟磁性粒子除外成分の動的粘弾性測定における昇温速度１０℃／分、周波数１Ｈｚでの１６０℃の引張貯蔵弾性率Ｅ´が、５．５×１０８Ｐａ以上である［１］～［３］のいずれかに記載の軟磁性フィルム
である。 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. A soft magnetic film in which a volume ratio of particles is 65% by volume or more in terms of solid content, and a porosity of the soft magnetic film is 2.5% by volume or less,
[2] The soft magnet according to [1], wherein the resin component contains a polyfunctional monomer type epoxy resin, a phenol resin, and an acrylic resin, and a volume ratio of the acrylic resin to the resin component is 10% by volume or less. the film,
[3] The soft magnetic film according to [2], wherein the acrylic resin has a glass transition temperature of 0 ° C. or higher.
[4] Tensile storage elastic modulus E ′ at 160 ° C. at a rate of temperature increase of 10 ° C./min and a frequency of 1 Hz in dynamic viscoelasticity measurement of a component excluding the soft magnetic particles from the soft magnetic resin composition. Is the soft magnetic film according to any one of [1] to [3], which is 5.5 × 10 8 Pa or more.
　本発明の軟磁性フィルムによれば、高い割合で軟磁性粒子が含有されており、耐リフロー性に優れる。 According to the soft magnetic film of the present invention, soft magnetic particles are contained in a high ratio, and the reflow resistance is excellent.
図１は、本発明の軟磁性フィルムの一実施形態を備える軟磁性積層回路基板の断面図を示す。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.
　本発明の軟磁性フィルムは、例えば、軟磁性粒子および樹脂成分を含有する軟磁性樹脂組成物からフィルム状（シート状）に形成される。 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.
　軟磁性粒子を構成する軟磁性材料としては、例えば、磁性ステンレス（Ｆｅ－Ｃｒ－Ａｌ－Ｓｉ合金）、センダスト（Ｆｅ－Ｓｉ－Ａ１合金）、パーマロイ（Ｆｅ－Ｎｉ合金）、ケイ素銅（Ｆｅ－Ｃｕ－Ｓｉ合金）、Ｆｅ－Ｓｉ合金、Ｆｅ－Ｓｉ―Ｂ（－Ｃｕ－Ｎｂ）合金、Ｆｅ－Ｓｉ－Ｃｒ－Ｎｉ合金、Ｆｅ－Ｓｉ－Ｃｒ合金、Ｆｅ－Ｓｉ－Ａｌ－Ｎｉ－Ｃｒ合金、フェライトなどが挙げられる。これらの中でも、磁気特性の点から、好ましくは、センダスト（Ｆｅ－Ｓｉ－Ａｌ合金）が挙げられる。 Examples of the soft magnetic material constituting the soft magnetic particles 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. Among these, Sendust (Fe—Si—Al alloy) is preferable from the viewpoint of magnetic properties.
　軟磁性粒子は、扁平状（板状）に形成されている、すなわち、厚みが薄くて面が広い形状に形成されている。軟磁性粒子の扁平率（扁平度）は、例えば、８以上、好ましくは、１５以上であり、また、例えば、８０以下、好ましくは、６５以下である。扁平率は、例えば、軟磁性粒子の平均粒子径（平均長さ）を軟磁性粒子の平均厚さで除したアスペクト比として算出される。　　 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. *
　軟磁性粒子の平均粒子径（平均長さ）は、例えば、３．５μｍ以上、好ましくは、１０μｍ以上であり、また、例えば、１００μｍ以下、好ましくは、８０μｍ以下である。平均厚みは、例えば、０．３μｍ以上、好ましくは、０．５μｍ以上であり、また、例えば、３μｍ以下、好ましくは、２．５μｍ以下である。軟磁性粒子の扁平率、平均粒子径、平均厚みなどを調整することにより、軟磁性粒子による反磁界の影響を小さくでき、その結果、軟磁性粒子の透磁率を増加させることができる。なお、軟磁性粒子の大きさを均一にするために、必要に応じて、ふるいなどを使用して分級された軟磁性粒子を用いてもよい。 The average particle diameter (average length) of the soft magnetic particles is, for example, 3.5 μm or more, preferably 10 μm or more, and for example, 100 μm or less, preferably 80 μm or less. The average thickness is, for example, 0.3 μm or more, preferably 0.5 μm or more, and for example, 3 μm or less, preferably 2.5 μm or less. By adjusting the flatness, average particle diameter, average thickness, etc. of the soft magnetic particles, the influence of the demagnetizing field due to the soft magnetic particles can be reduced, and as a result, the magnetic permeability of the soft magnetic particles can be increased. In order to make the size of the soft magnetic particles uniform, soft magnetic particles classified using a sieve or the like may be used as necessary.
　軟磁性粒子の比重は、例えば、５．０以上８．０以下である。 The specific gravity of the soft magnetic particles is, for example, 5.0 or more and 8.0 or less.
　軟磁性樹脂組成物における軟磁性粒子の体積割合は、固形分換算で、例えば、６５体積％以上、好ましくは、７０体積％以上であり、例えば、９５体積％以下、好ましくは、９０体積％以下である。また、質量割合は、固形分換算で、例えば、８５質量％を超過し、好ましくは、８８質量％以上、より好ましくは、９０質量％以上であり、また、例えば、９８質量％以下、好ましくは、９５質量％以下である。軟磁性粒子の含有割合を上記下限以上とすることにより、軟磁性フィルムの磁気特性が優れる。一方、上記上限以下とすることにより、軟磁性樹脂組成物の成膜性が優れる。 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. By setting the content ratio of the soft magnetic particles to the above lower limit or more, the magnetic properties of the soft magnetic film are excellent. On the other hand, the film forming property of the soft magnetic resin composition is excellent by setting the upper limit or less.
　なお、軟磁性粒子などの各成分の体積割合は、各成分の質量をその成分の比重で除した理論体積を元に算出される。各成分の比重は、カタログ値または公知の測定方法（例えば、後述する比重測定法）によって得られる。 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).
　樹脂成分は、好ましくは、熱硬化性樹脂およびアクリル樹脂を含有する。より好ましくは、エポキシ樹脂およびフェノール樹脂からなる熱硬化性樹脂と、アクリル樹脂とを含有する。 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.
　エポキシ樹脂としては、好ましくは、繰り返し単位として２つ以上の官能基（グリシジル基など）を有する多官能モノマーから構成されるエポキシ樹脂（多官能モノマー型エポキシ樹脂）などが挙げられる。 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.
　多官能モノマー型エポキシとしては、好ましくは、トリスヒドロキシフェニルメタン型エポキシ樹脂、テトラフェニロールエタン型エポキシ樹脂などが挙げられる。好ましくは、トリスヒドロキシフェニルメタン型エポキシ樹脂が挙げられる。具体的には、下記一般式（１）で表されるトリスヒドロキシフェニルメタン型エポキシ樹脂などが挙げられる。 The polyfunctional monomer type epoxy is preferably a trishydroxyphenylmethane type epoxy resin, a tetraphenylolethane type epoxy resin, or the like. Preferably, a trishydroxyphenylmethane type epoxy resin is used. Specific examples include trishydroxyphenylmethane type epoxy resin represented by the following general formula (1).
Figure JPOXMLDOC01-appb-C000001
Figure JPOXMLDOC01-appb-C000001
　なお、ｎは、モノマーの重合度を示す。 Note that n represents the degree of polymerization of the monomer.
　熱硬化性樹脂として多官能モノマー型エポキシ樹脂を含有することにより、溶融温度を低くでき、かつ、後述するフェノール樹脂と密に架橋硬化できる。そのため、軟磁性粒子を高い含有割合（例えば、６５体積％以上）で含有する軟磁性樹脂組成物を圧縮し、高充填率の軟磁性フィルムを作製する際に、軟磁性粒子同士の反発力による樹脂組成物内の亀裂ひいては空隙の発生（スプリングバック）を抑制することができ、より確実に低い空隙率の軟磁性フィルムを作製することができる。 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.
　エポキシ樹脂のエポキシ当量は、例えば、１０ｇ／ｅｑ．以上、好ましくは、１００ｇ／ｅｑ．以上であり、また、例えば、５００ｇ／ｅｑ．以下、好ましくは、１８０ｇ／ｅｑ．以下である。 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.
　エポキシ樹脂の粘度（１５０℃）は、例えば、１．０Ｐａ・ｓ以下、好ましくは、０．２Ｐａ・ｓ以下であり、また、０．０１Ｐａ・ｓ以上である。粘度は、ＩＣＩ粘度計により測定される。 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.
　エポキシ樹脂の比重は、例えば、１．０以上１．５以下である。 The specific gravity of the epoxy resin is, for example, 1.0 or more and 1.5 or less.
　フェノール樹脂は、エポキシ樹脂の硬化剤となる熱硬化性樹脂であって、例えば、フェノールノボラック樹脂、クレゾールノボラック樹脂、フェノールアラルキル樹脂、フェノールビフェニレン樹脂、ジシクロペンタジエン型フェノール樹脂、レゾール樹脂が挙げられる。これらは単独使用また２種以上を併用することができる。 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.
　これらのフェノール樹脂のうち、好ましくは、フェノールノボラック樹脂が挙げられる。繰り返し単位に官能基を複数有する多官能モノマー型エポキシ樹脂に対して、架橋点距離を短くすることができるフェノールノボラック樹脂を使用することにより、多官能モノマー型エポキシ樹脂とフェノールノボラック樹脂とが互に密に多く架橋することができ、より高強度の硬化樹脂を得ることができる。このため、軟磁性粒子のスプリングバックを確実に抑制し、特に低い空隙率の軟磁性フィルムを得ることができる。 Of these phenol resins, a phenol novolac resin is preferable. By using 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.
　フェノール樹脂の水酸基当量は、例えば、１０ｇ／ｅｑ．以上、好ましくは、８０ｇ／ｅｑ．以上であり、また、例えば、５００ｇ／ｅｑ．以下、好ましくは、１５０ｇ／ｅｑ．以下である。 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.
　フェノール樹脂の粘度（１５０℃）は、例えば、０．１０Ｐａ・ｓ以下、好ましくは、０．０４Ｐａ・ｓ以下であり、また、０．０１Ｐａ・ｓ以上である。 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.
　フェノール樹脂の比重は、例えば、１．０以上１．５以下である。 The specific gravity of the phenol resin is, for example, 1.0 or more and 1.5 or less.
　アクリル樹脂としては、例えば、直鎖もしくは分岐のアルキル基を有する（メタ）アクリル酸アルキルエステルの１種または２種以上をモノマー成分とし、そのモノマー成分を重合することにより得られるアクリル系重合体などが挙げられる。なお、「（メタ）アクリル」は、「アクリルおよび／またはメタクリル」を表す。 As 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. Is mentioned. Note that “(meth) acryl” means “acryl and / or methacryl”.
　アルキル基としては、例えば、メチル基、エチル基、プロピル基、イソプロピル基、ｎ－ブチル基、ｔ－ブチル基、イソブチル基、アミル基、イソアミル基、ヘキシル基、へプチル基、シクロヘキシル基、２－エチルヘキシル基、オクチル基、イソオクチル基、ノニル基、イソノニル基、デシル基、イソデシル基、ウンデシル基、ラウリル基、トリデシル基、テトラデシル基、ステアリル基、オクタデシル基、ドデシル基などの炭素数１～２０のアルキル基が挙げられる。好ましくは、炭素数１～６のアルキル基が挙げられる。 Examples of the alkyl group 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. Preferably, an alkyl group having 1 to 6 carbon atoms is used.
　アクリル系重合体は、（メタ）アクリル酸アルキルエステルとその他のモノマーとの共重合体であってもよい。 The acrylic polymer may be a copolymer of (meth) acrylic acid alkyl ester and other monomers.
　その他のモノマーとしては、例えば、グリシジルアクリレート、グリシジルメタクリレートなどのグリシジル基含有モノマー、例えば、アクリル酸、メタクリル酸、カルボキシエチルアクリレート、カルボキシペンチルアクリレート、イタコン酸、マレイン酸、フマール酸、クロトン酸などカルボキシル基含有モノマー、例えば、無水マレイン酸、無水イタコン酸などの酸無水物モノマー、例えば、（メタ）アクリル酸２－ヒドロキシエチル、（メタ）アクリル酸２－ヒドロキシプロピル、（メタ）アクリル酸４－ヒドロキシブチル、（メタ）アクリル酸６－ヒドロキシヘキシル、（メタ）アクリル酸８－ヒドロキシオクチル、（メタ）アクリル酸１０－ヒドロキシデシル、（メタ）アクリル酸１２－ヒドロキシラウリルまたは（４－ヒドロキシメチルシクロヘキシル）－メチルアクリレートなどのヒドロキシル基含有モノマー、例えば、スチレンスルホン酸、アリルスルホン酸、２－（メタ）アクリルアミド－２－メチルプロパンスルホン酸、（メタ）アクリルアミドプロパンスルホン酸、スルホプロピル（メタ）アクリレート、（メタ）アクリロイルオキシナフタレンスルホン酸などのスルホン酸基含有モノマー、２－ヒドロキシエチルアクリロイルホスフェートなど燐酸基含有モノマー、例えば、スチレンモノマー、例えば、アクリロニトリルなどが挙げられる。これらは単独使用または２種以上を併用することができる。これらの中でも、好ましくは、アクリロニトリルが挙げられる。 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. Containing monomers, for example, 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 (meth) acryloyloxynaphthalene sulfonic acid, phosphoric acid group-containing monomer such as 2-hydroxyethylacryloyl phosphate, for example, styrene monomer such as acrylonitrile. These can be used alone or in combination of two or more. Among these, Preferably, an acrylonitrile is mentioned.
　また、アクリル樹脂は、好ましくは、エポキシ基を有する。アクリル樹脂がエポキシ基を有する場合、エポキシ価は、例えば、１０ｅｑ．／ｇ以上、好ましくは、１００ｅｑ．／ｇ以上であり、また、例えば、８００ｅｑ．／ｇ以下、好ましくは、５００ｅｑ．／ｇ以下である。 The acrylic resin preferably has an epoxy group. When the acrylic resin 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.
　アクリル樹脂の重量平均分子量は、例えば、１×１０５以上、好ましくは、３×１０５以上であり、また、例えば、１×１０６以下である。なお、重量平均分子量は、ゲル浸透クロマトフラフィー（ＧＰＣ）により、標準ポリスチレン換算値により測定される。 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. In addition, a weight average molecular weight is measured by a standard polystyrene conversion value by gel permeation chromatography (GPC).
　アクリル樹脂のガラス転移温度（Ｔｇ）は、例えば、－２０℃以上、好ましくは、０℃以上、より好ましくは、１０℃以上、さらに好ましくは、１２℃以上である。また、例えば、５０℃以下、好ましくは、３０℃以下である。アクリル樹脂のＴｇを上記下限以上とすることにより、樹脂成分の強度を向上させ、スプリングバックを抑制し、空隙率を低くすることができる。また、軟磁性フィルムの取扱い、半硬化状態における軟磁性熱硬化性フィルムの接着性が優れる。なお、ガラス転移温度は、動的粘弾性測定装置（ＤＭＡ、周波数１Ｈｚ、引張モード、昇温速度１０℃／ｍｉｎ）を用いて測定される損失正接（ｔａｎδ）の極大値により得られる。 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. By making Tg of acrylic resin more than the said minimum, the intensity | strength of a resin component can be improved, a springback can be suppressed and a porosity can be made low. In addition, 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 δ) measured using a dynamic viscoelasticity measuring device (DMA, frequency 1 Hz, tensile mode, heating rate 10 ° C./min).
　アクリル樹脂の比重は、例えば、０．６以上１．０以下である。 The specific gravity of the acrylic resin is, for example, 0.6 or more and 1.0 or less.
　樹脂成分は、熱硬化性樹脂およびアクリル樹脂以外のその他の樹脂を含有することもできる。 The resin component can also contain other resins other than the thermosetting resin and the acrylic resin.
　このような樹脂としては、例えば、天然ゴム、ブチルゴム、イソプレンゴム、クロロプレンゴム、エチレン－酢酸ビニル共重合体、ポリブタジエン樹脂、ポリカーボネート樹脂、熱可塑性ポリイミド樹脂、ポリアミド樹脂（６－ナイロン、６，６－ナイロンなど）、フェノキシ樹脂、飽和ポリエステル樹脂（ＰＥＴ、ＰＢＴなど）、ポリアミドイミド樹脂、フッ素樹脂などが挙げられる。これらは単独使用または２種以上を併用することができる。 Examples of 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.
　軟磁性樹脂組成物における樹脂成分の体積割合は、固形分換算で、例えば、５体積％以上、好ましくは、１０体積％以上であり、また、例えば、３５体積％以下、好ましくは、３０体積％以下である。軟磁性樹脂組成物における樹脂成分の質量割合は、固形分換算で、例えば、２質量％以上、好ましくは、５質量％以上であり、また、例えば、１５質量％未満、好ましくは、１２質量％以下、より好ましくは、１０質量％以下である。樹脂成分の含有割合が上記範囲内であることにより、軟磁性フィルムの成膜性、磁気特性に優れる。 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. When the content ratio of the resin component is within the above range, the soft magnetic film is excellent in film formability and magnetic characteristics.
　樹脂成分における熱硬化性樹脂（好ましくは、エポキシ樹脂およびフェノール樹脂からなる熱硬化性樹脂）の体積割合は、例えば、８５体積％以上、好ましくは、９０体積％以上、より好ましくは、９５体積％以上であり、また、例えば、９９体積％以下、好ましくは、９７体積％以下である。 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.
　樹脂成分におけるエポキシ樹脂の体積割合は、例えば、１０体積％以上、好ましくは、３０体積％以上、より好ましくは、５０体積％を超過し、また、例えば、９０体積％以下、好ましくは、８０体積％以下、より好ましくは、７０体積％以下である。樹脂成分におけるエポキシ樹脂の質量割合は、例えば、１０質量％以上、好ましくは、３０質量％以上、より好ましくは、５０質量％を超過し、また、例えば、９０質量％以下、好ましくは、８０質量％以下、より好ましくは、７０質量％以下である。 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.
　樹脂成分におけるフェノール樹脂の体積割合は、例えば、１０体積％以上、好ましくは、２０体積％以上、より好ましくは、３０体積％を超過し、また、例えば、９０体積％以下、好ましくは、７０体積％以下、より好ましくは、５０体積％未満である。樹脂成分におけるフェノール樹脂の質量割合は、例えば、１０質量％以上、好ましくは、２０質量％以上、より好ましくは、３０質量％を超過し、また、例えば、９０質量％以下、好ましくは、７０質量％以下、より好ましくは、５０質量％未満である。 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.
　また、エポキシ樹脂１００体積部に対するフェノール樹脂の含有割合は、例えば、１０体積部以上、好ましくは、５０体積部以上であり、また、例えば、２００体積部以下、好ましくは、１００体積部未満である。 Moreover, 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. .
　樹脂成分におけるアクリル樹脂の体積割合は、例えば、１体積％以上、好ましくは、３体積％以上であり、また、例えば、２５体積％以下、好ましくは、１５体積％以下、より好ましくは、１０体積％以下、さらに好ましくは、５体積％以下である。樹脂成分におけるアクリル樹脂の質量割合は、例えば、１質量％以上、好ましくは、３質量％以上であり、また、例えば、２５質量％以下、好ましくは、１５質量％以下、より好ましくは、１０質量％以下、さらに好ましくは、５質量％以下である。アクリル樹脂の含有割合が上記範囲内である場合、軟磁性フィルムの空隙率をより低くすることができる。 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. When the content ratio of the acrylic resin is within the above range, the porosity of the soft magnetic film can be further reduced.
　軟磁性樹脂組成物は、好ましくは、熱硬化触媒を含有する。 The soft magnetic resin composition preferably contains a thermosetting catalyst.
　熱硬化触媒としては、加熱により樹脂成分の硬化を促進する触媒であれば限定的でなく、例えば、イミダゾール系化合物、トリフェニルフォスフィン系化合物、トリフェニルボラン系化合物、アミノ基含有化合物などが挙げられる。好ましくは、イミダゾール系化合物が挙げられる。 The 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.
　イミダゾール系化合物としては、例えば、２－フェニルイミダゾール（商品名；２ＰＺ）、２－エチル－４－メチルイミダゾール（商品名；２Ｅ４ＭＺ）、２－メチルイミダゾール（商品名；２ＭＺ）、２－ウンデシルイミダゾール（商品名；Ｃ１１Ｚ）、２－フェニル－１Ｈ－イミダゾール４，５－ジメタノール（商品名；２ＰＨＺ－ＰＷ）、２，４－ジアミノ－６－（２’－メチルイミダゾリル（１）’）エチル－ｓ－トリアジン・イソシアヌール酸付加物（商品名；２ＭＡＯＫ－ＰＷ）などが挙げられる（上記商品名は、いずれも四国化成社製）。これらは単独使用または２種以上を併用することができる。 Examples of imidazole compounds 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.
　熱硬化触媒の比重は、例えば、０．９以上１．５以下である。 The specific gravity of the thermosetting catalyst is, for example, 0.9 or more and 1.5 or less.
　熱硬化触媒の含有割合は、樹脂成分１００体積部に対して、例えば、０．１体積部以上、好ましくは、０．３体積部以上であり、また、例えば、５体積部以下、好ましくは、３体積部以下である。熱硬化触媒の質量割合は、樹脂成分１００質量部に対して、例えば、０．１質量部以上、好ましくは、０．３質量部以上であり、また、例えば、５質量部以下、好ましくは、３質量部以下である。熱硬化触媒の含有割合を上記範囲内とすることにより、軟磁性樹脂組成物を低温度かつ短時間で加熱硬化することができ、また、耐リフロー性に優れる。 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. By setting the content ratio of the thermosetting catalyst within the above range, the soft magnetic resin composition can be heat-cured at a low temperature and in a short time, and is excellent in reflow resistance.
　軟磁性樹脂組成物は、レオロジーコントロール剤を含有することもできる。軟磁性樹脂組成物がレオロジーコントロール剤を含有することにより、軟磁性粒子を軟磁性フィルム中により均一に分散させることができる。 The soft magnetic resin composition can also contain a rheology control agent. When the soft magnetic resin composition contains a rheology control agent, the soft magnetic particles can be more uniformly dispersed in the soft magnetic film.
　レオロジーコントロール剤は、せん断力（せん断速度）が低い場合には高粘度を示し、せん断力（せん断速度）が高い場合には低粘度を示すチキソトロピック性を軟磁性樹脂組成物に付与する化合物である。 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.
　レオロジーコントロール剤としては、例えば、有機系レオロジーコントロール剤および無機系レオロジーコントロール剤が挙げられる。好ましくは、有機系レオロジーコントロール剤が挙げられる。 Examples of the rheology control agent include organic rheology control agents and inorganic rheology control agents. Preferably, an organic rheology control agent is used.
　有機系レオロジーコントロール剤としては、例えば、変性ウレア、ウレア変性ポリアマイド、脂肪酸アマイド、ポリウレタン、高分子ウレア誘導体などが挙げられる。好ましくは、変性ウレア、ウレア変性ポリアマイド、脂肪酸アマイドが挙げられ、より好ましくは、ウレア変性ポリアマイドが挙げられる。 Examples of the organic rheology control agent 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.
　無機系レオロジーコントロール剤としては、例えば、シリカ、炭酸カルシウム、スメクタイトなどが挙げられる。 Examples of the inorganic rheology control agent include silica, calcium carbonate, smectite and the like.
　レオロジーコントロール剤としては、具体的には、例えば、ビックケミー社の「ＢＹＫ－４１０」、「ＢＹＫ－４３０」、「ＢＹＫ－４３１」、例えば、楠本化成社の「ディスパロンＰＦＡ－１３１」、例えば、日本アエロジル社の「アエロジル　ＶＰ　ＮＫ２００」、「アエロジル　Ｒ９７６Ｓ」、「アエロジル　ＣＯＫ８４」などが挙げられる。 Specific examples of the rheology control agent 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.
　これらは単独使用または２種以上を併用することができる。 These can be used alone or in combination of two or more.
　レオロジーコントロール剤の比重は、例えば、０．６以上１．０以下である。 The specific gravity of the rheology control agent is, for example, 0.6 or more and 1.0 or less.
　レオロジーコントロール剤の体積割合は、樹脂成分１００体積部に対して、例えば、０．１体積部以上、好ましくは、１体積部以上であり、また、例えば、１０体積部以下、好ましくは、５体積部以下である。レオロジーコントロール剤の質量割合は、樹脂成分１００質量部に対して、例えば、０．１質量部以上、好ましくは、１質量部以上であり、また、例えば、１０質量部以下、好ましくは、５質量部以下である。 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.
　軟磁性樹脂組成物は、さらに必要に応じて、その他の添加剤を含有することもできる。添加剤としては、例えば、分散剤、架橋剤、無機充填材などの市販または公知のものが挙げられる。 The soft magnetic resin composition may further contain other additives as necessary. As an additive, commercially available or well-known things, such as a dispersing agent, a crosslinking agent, an inorganic filler, are mentioned, for example.
　軟磁性樹脂組成物から軟磁性粒子を除外した軟磁性粒子除外成分の動的粘弾性測定における昇温速度１０℃／分、周波数１Ｈｚでの１６０℃の引張貯蔵弾性率Ｅ´は、例えば、５．５×１０８Ｐａ以上、好ましくは、８．０×１０８Ｐａ以上であり、また、例えば、３．０×１０９Ｐａ以下、好ましくは、１．０×１０９Ｐａ以下である。軟磁性粒子除外成分の引張貯蔵弾性率Ｅ´が上記範囲内である場合、軟磁性フィルムの空隙率をより低くすることができる。引張貯蔵弾性率Ｅ´は、実施例にて詳述する。 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. When 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.
　軟磁性樹脂組成物は、上記成分を上記含有割合で混合することにより調製される。 The soft magnetic resin composition is prepared by mixing the above components in the above content ratio.
　軟磁性フィルムは、例えば、軟磁性樹脂組成物を溶媒に溶解または分散させることにより、軟磁性樹脂組成物溶液を調製する調製工程、離型基材の表面に塗布し、乾燥させることにより、半硬化状態の軟磁性熱硬化性フィルムを得る乾燥工程、および、軟磁性熱硬化性フィルムを複数枚積層し、熱プレスする熱プレス工程により、製造することができる。 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.
　まず、軟磁性樹脂組成物を溶媒に溶解または分散させる（調製工程）。これにより、軟磁性樹脂組成物溶液を調製する。 First, the soft magnetic resin composition is dissolved or dispersed in a solvent (preparation step). Thereby, a soft magnetic resin composition solution is prepared.
　溶媒としては、例えば、アセトン、メチルエチルケトン（ＭＥＫ）などケトン類、例えば、酢酸エチルなどのエステル類、例えば、プロピレングリコールモノメチルエーテルなどのエーテル類、例えば、Ｎ，Ｎ－ジメチルホルムアミドなどのアミド類などの有機溶媒などが挙げられる。また、溶媒として、例えば、水、例えば、メタノール、エタノール、プロパノール、イソプロパノールなどのアルコールなどの水系溶媒も挙げられる。 Examples of the solvent 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. An organic solvent etc. are mentioned. Examples of the solvent also include aqueous solvents such as water, for example, alcohols such as methanol, ethanol, propanol, and isopropanol.
　軟磁性樹脂組成物溶液における固形分量は、例えば、１０質量％以上、好ましくは、３０質量％以上であり、また、例えば、９０質量％以下、好ましくは、７０質量％以下である。 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.
　次いで、軟磁性樹脂組成物溶液を、離型基材（セパレータ、コア材など）の表面に塗布し、乾燥させる（乾燥工程）。 Next, the soft magnetic resin composition solution is applied to the surface of a release substrate (separator, core material, etc.) and dried (drying step).
　塗布方法としては特に限定されず、例えば、ドクターブレード法、ロール塗工、スクリーン塗工、グラビア塗工などが挙げられる。 Application method is not particularly limited, and examples thereof include a doctor blade method, roll coating, screen coating, and gravure coating.
　乾燥条件としては、乾燥温度は、例えば、７０℃以上１６０℃以下であり、乾燥時間は、例えば、１分以上５分以下である。 As drying conditions, the drying temperature is, for example, 70 ° C. or more and 160 ° C. or less, and the drying time is, for example, 1 minute or more and 5 minutes or less.
　セパレータとしては、例えば、ポリエチレンテレフタレート（ＰＥＴ）フィルム、ポリエチレンフィルム、ポリプロピレンフィルム、紙などが挙げられる。これらは、その表面に、例えば、フッ素系剥離剤、長鎖アルキルアクリレート系剥離剤、シリコーン系剥離剤などにより離型処理されている。 Examples of the separator 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.
　コア材としては、例えば、プラスチックフィルム（例えば、ポリイミドフィルム、ポリエステルフィルム、ポリエチレンテレフタレートフィルム、ポリエチレンナフタレートフィルム、ポリカーボネートフィルムなど）、金属フィルム（例えば、アルミウム箔など）、例えば、ガラス繊維やプラスチック製不織繊維などで強化された樹脂基板、シリコーン基板、ガラス基板などが挙げられる。 Examples of the core material 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.
　セパレータまたはコア材の平均厚みは、例えば、１μｍ以上５００μｍ以下である。 The average thickness of the separator or core material is, for example, 1 μm or more and 500 μm or less.
　これにより、半硬化状態（Ｂステージ状態）の軟磁性熱硬化性フィルムを得る。 Thereby, a soft magnetic thermosetting film in a semi-cured state (B stage state) is obtained.
　軟磁性熱硬化性フィルムの平均厚みは、例えば、５μｍ以上、好ましくは、５０μｍ以上であり、また、例えば、５００μｍ以下、好ましくは、２５０μｍ以下である。 The average thickness of the soft magnetic thermosetting film is, for example, 5 μm or more, preferably 50 μm or more, and for example, 500 μm or less, preferably 250 μm or less.
　次いで、得られた軟磁性熱硬化性フィルムを複数枚用意し、複数枚の軟磁性熱硬化性フィルムを熱プレスにより、厚み方向に熱プレスする（熱プレス工程）。これにより、半硬化状態の軟磁性熱硬化性フィルムが加熱硬化される。また、軟磁性フィルム内に軟磁性粒子を高割合で充填させ、磁気特性を向上させることができる。 Next, a plurality of the obtained 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). As a result, the semi-cured soft magnetic thermosetting film is cured by heating. In addition, the soft magnetic film can be filled with soft magnetic particles at a high ratio to improve the magnetic properties.
　熱プレスは、公知のプレス機を用いて実施することができ、例えば、平行平板プレス機などが挙げられる。 The hot press can be performed using a known press machine, for example, a parallel plate press machine.
　軟磁性熱硬化性フィルムの積層枚数は、例えば、２層以上であり、また、例えば、２０層以下、好ましくは、５層以下である。これにより、所望の厚みの軟磁性フィルムに調整することができる。 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.
　加熱温度は、例えば、８０℃以上、好ましくは、１００℃以上であり、また、例えば、２００℃以下、好ましくは、１８０℃以下である。 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.
　加熱時間は、例えば、０．１時間以上、好ましくは、０．２時間以上であり、また、例えば、２４時間以下、好ましくは、２時間以下である。 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.
　圧力は、例えば、１０ＭＰａ以上、好ましくは、２０ＭＰａ以上であり、また、例えば、５００ＭＰａ以下、好ましくは、２００ＭＰａ以下である。 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.
　これにより、軟磁性熱硬化性フィルムが加熱硬化され、硬化状態（Ｃステージ状態）の軟磁性フィルムが得られる。 Thereby, the soft magnetic thermosetting film is cured by heating to obtain a soft magnetic film in a cured state (C stage state).
　この軟磁性フィルムの平均厚みは、例えば、５μｍ以上、好ましくは、５０μｍ以上であり、また、例えば、５００μｍ以下、好ましくは、２５０μｍ以下である。 The average thickness of the soft magnetic film is, for example, 5 μm or more, preferably 50 μm or more, and for example, 500 μm or less, preferably 250 μm or less.
　軟磁性フィルムの空隙率は、２．５体積％未満である。好ましくは、２．０体積％未満、より好ましくは、１．０体積％未満である。これにより、軟磁性フィルムの耐リフロー性が優れる。 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.
　空隙率は、下記式により測定される。 The porosity is measured by the following formula.
　空隙率（％）＝｛１－（比重（Ｓ．Ｇ．））／（理論比重）｝×１００
　比重（Ｓ．Ｇ．）は、電子分析天秤（島津製作所社製、「ＡＥＬ－２００」）を用いて、比重測定法により、空気中での軟磁性フィルムの重さＷ１（ｇ）および水中での軟磁性フィルムＷ２の重さ（ｇ）を測定して、下記式により算出される。 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.
　　比重（Ｓ．Ｇ．）＝Ｗ１／（Ｗ１－Ｗ２）
　理論比重は、例えば、軟磁性フィルムを形成する軟磁性樹脂組成物に含まれる固形分成分(軟磁性粒子、樹脂成分、必要に応じて添加される熱硬化触媒、レオロジーコントロール剤およびその他の添加剤など)について、各固形分成分の比重のそれぞれを各固形分成分の配合割合（重量）のそれぞれで乗じ、それらを足し合わせることにより得られる。なお、各固形分成分の比重（例えば、軟磁性粒子）は、カタログ値などを参照することができる。 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. In addition, the catalog value etc. can be referred for the specific gravity (for example, soft magnetic particle) of each solid content component.
　また、軟磁性樹脂組成物の各固形分成分のうち、軟磁性粒子および樹脂成分が主成分を占める場合は、軟磁性フィルムの理論比重は、軟磁性粒子および樹脂成分のみからなる軟磁性フィルムにおける理論比重を代用することもできる。 In addition, when the soft magnetic particles and the resin component occupy the main components among the solid content components of the soft magnetic resin composition, 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.
　軟磁性フィルムの理論比重は、例えば、２．０以上、好ましくは、２．２以上であり、また、例えば、８．０以下、好ましくは、６．０以下である。 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.
　軟磁性フィルムの比透磁率μ´は、例えば、１５０以上、好ましくは、１８０以上であり、また、例えば、５００以下である。比透磁率μ´は、インピーダンスアナライザー（Ａｇｉｌｅｎｔ社製、「４２９４Ａ」）を用いて、１ターン法（周波数１ＭＨｚ）によって測定される。 The relative magnetic permeability μ ′ of the soft magnetic film is, for example, 150 or more, preferably 180 or more, and for example, 500 or less. The relative permeability μ ′ is measured by a one-turn method (frequency 1 MHz) using an impedance analyzer (manufactured by Agilent, “4294A”).
　軟磁性フィルムは、好ましくは、軟磁性フィルムに含有される扁平状軟磁性粒子が、軟磁性フィルムの２次元の面内方向に配列されている。すなわち、扁平状軟磁性粒子の長手方向（厚み方向と直交する方向）が軟磁性フィルムの面方向に沿うように配向している。これにより、軟磁性フィルムは、軟磁性粒子が高割合で充填され、磁気特性に優れる。また、軟磁性フィルムの薄膜化が図られている。 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.
　この軟磁性フィルムは、例えば、軟磁性フィルムの単層のみからなる単層構造、コア材の片面または両面に軟磁性フィルムが積層された多層構造、軟磁性フィルムの片面または両面にセパレータが積層された多層構造などの形態とすることができる。 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.
　また、上記の実施形態では、軟磁性熱硬化性フィルムを複数枚積層させて熱プレスしたが、例えば、軟磁性熱硬化性フィルム１枚（単層）に対して熱プレスを実施してもよい。 In the above embodiment, a plurality of soft magnetic thermosetting films are laminated and hot pressed. For example, one soft magnetic thermosetting film (single layer) may be hot pressed. .
　そして、軟磁性フィルムによれば、扁平状の軟磁性粒子および樹脂成分を含有し、軟磁性樹脂組成物に対する軟磁性粒子の体積割合が、固形分換算で、６５体積％以上である軟磁性樹脂組成物から形成され、軟磁性フィルムの空隙率が、２．５体積％以下であるため、軟磁性フィルムにおいて、軟磁性粒子が高充填率（高密度）で含まれている。また、軟磁性フィルムの空隙率が、２．５体積％以下であるため、耐リフロー性に優れ、リフロー工程後によって発生ないし膨張する空隙を抑制することができる。 According to the soft magnetic film, 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 | gap which generate | occur | produces or expand | swells after a reflow process can be suppressed.
　よって、軟磁性フィルムは、リフロー工程後においても、軟磁性フィルムの剥離や外観不良を抑制できる。また、良好な磁気特性を発揮することができる。 Therefore, 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.
　この軟磁性フィルムは、例えば、アンテナ、コイル、またはこれらが表面に形成された回路基板に積層するための軟磁性フィルムとして好適に用いることができる。 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.
　具体的には、この軟磁性フィルムは、例えば、図１に示すように、回路基板２と、回路基板２の下面（一方面）に配置される接着剤層３と、接着剤層３の下面に配置される軟磁性フィルム４とを備える軟磁性フィルム積層基板１として用いることができる。 Specifically, for example, as shown in FIG. 1, 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 | positioned.
　回路基板２は、例えば、電磁誘導方式で使用される回路基板２などであり、基板５の上面（一方面）に、ループコイルなどの配線パターン６が形成されている。配線パターン６は、セミアディティブ法またはサブトラクティブ法などによって形成される。 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.
　基板５を構成する絶縁材料としては、例えば、ガラスエポキシ基板、ガラス基板、ＰＥＴ基板、テフロン基板、セラミックス基板、ポリイミド基板などが挙げられる。 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.
　接着剤層３は、回路基板２の接着剤として通常使用される公知のものが用いられ、例えば、エポキシ系接着剤、ポリイミド系接着剤、アクリル系接着剤などの接着剤を塗布および乾燥することにより形成される。接着剤層３の厚みは、例えば、１０～１００μｍである。 As the adhesive layer 3, a known one that is usually used as an adhesive for the circuit board 2 is used. For example, 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 μm.
　軟磁性フィルム４は、上述の軟磁性フィルムであって、扁平状の軟磁性粒子７が軟磁性樹脂組成物（具体的には、樹脂成分が硬化した硬化樹脂８）中に分散されている。好ましくは、軟磁性粒子７は、その長手方向（厚み方向と直交する方向）が軟磁性フィルム４の面方向に沿うように配向している。 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). Preferably, 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.
　このような軟磁性フィルム積層基板１は、例えば、スマートフォン、パソコン、位置検出装置などの用途に用いることができる。 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.
　なお、図１の実施形態では、回路基板２と軟磁性フィルム４との間に接着剤層３が設けられているが、例えば、図示しないが、回路基板２に軟磁性フィルム４を直接接触するように設けることもできる。 In the embodiment of FIG. 1, the adhesive layer 3 is provided between the circuit board 2 and the soft magnetic film 4. For example, although not shown, the soft magnetic film 4 is in direct contact with the circuit board 2. It can also be provided.
　軟磁性フィルム４を回路基板２に直接積層させるためには、半硬化状態の軟磁性熱硬化性フィルムを回路基板２に直接貼着させた後、軟磁性熱硬化性フィルムを加熱硬化する。 In order to directly laminate the soft magnetic film 4 on the circuit board 2, 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.
　この軟磁性フィルム積層基板１によれば、軟磁性フィルム４を備えているため、リフロー後の軟磁性フィルム４内の空隙を抑制でき、軟磁性フィルム４の剥離や外観不良を抑制することができる。ひいては、磁気特性の低下を抑制することができる。 According to this soft magnetic film laminated substrate 1, since the soft magnetic film 4 is provided, the space | gap in the soft magnetic film 4 after reflow can be suppressed, and peeling of the soft magnetic film 4 and an external appearance defect can be suppressed. . As a result, it is possible to suppress a decrease in magnetic characteristics.
　リフロー工程における温度は、例えば、２００℃以上、好ましくは、２５０℃以上であり、また、例えば、５００℃以下、好ましくは、３００℃以下である。 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.
　リフロー保存時間は、例えば、１秒以上、好ましくは、５秒以上であり、また、例えば、１０分以下、好ましくは、５分以下である。 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.
　以下に実施例および比較例を示し、本発明をさらに具体的に説明するが、本発明は、何ら実施例および比較例に限定されない。また、以下の記載において用いられる配合割合（含有割合）、物性値、パラメータなどの具体的数値は、上記の「発明を実施するための形態」において記載されている、それらに対応する配合割合（含有割合）、物性値、パラメータなど該当記載の上限値(「以下」、「未満」として定義されている数値）または下限値(「以上」、「超過」として定義されている数値）に代替することができる。 Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. However, the present invention is not limited to the examples and comparative examples. In addition, specific numerical values such as a blending ratio (content ratio), physical property values, and parameters used in the following description are described in the above-mentioned “Mode for Carrying Out the Invention”, and a blending ratio corresponding to them ( Substituting the upper limit value (numerical value defined as “less than” or “less than”) or the lower limit value (number defined as “greater than” or “exceeded”) such as content ratio), physical property values, parameters, etc. be able to.
　　実施例１
　軟磁性樹脂組成物に対し軟磁性粒子の体積割合が固形分換算で７０．０体積％となるように、Ｆｅ－Ｓｉ－Ａｌ合金５００質量部（７０．０体積％、以下の体積％は固形分を示す。）、トリスヒドロキシフェニルメタン型エポキシ樹脂（ＥＰＰＮ－５０１ＨＹ）２１．９質量部（１７．０体積％）、フェノールノボラック樹脂（ＬＶＲ８２１０ＤＬ）１３．５質量部（１０．４体積％）、アクリル酸エステル系共重合体溶液（ＳＧ－Ｐ３）８．６質量部（１．４体積％）、イミダゾール系化合物（熱硬化触媒、２ＰＨＺ－ＰＷ）０．３６質量部（０．２体積％）、および、ウレア変性ポリアマイド溶液（レオロジーコントロール剤、ＢＹＫ４３０）３．０質量部（１．０体積％）を混合することにより、軟磁性樹脂組成物を得た。 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).
　この軟磁性樹脂組成物をメチルエチルケトンに溶解させることにより、固形分濃度４０質量％の軟磁性樹脂組成物溶液を調製した。 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.
　この軟磁性樹脂組成物溶液を、セパレータ（シリコーン離型処理したポリエチレンテレフタレートフィルム）上に塗布し、その後、１３０℃で２分間乾燥させた。これにより、半硬化状態の軟磁性熱硬化性フィルム（平均厚み５０μｍ）を製造した。 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 μm) was produced.
　次いで、この軟磁性熱硬化性フィルムを、３層積層し、１６０℃、３０分、１６０ＭＰａの条件で熱プレスにて加熱硬化させることにより、完全硬化状態の軟磁性フィルム（平均厚み１５０μｍ）を作製した。 Next, three layers of this soft magnetic thermosetting film are 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 μm). did.
　　実施例２
　表１に記載の材料および配合割合で、軟磁性樹脂組成物を得た。軟磁性樹脂組成物を用いた以外は、実施例１と同様にして、実施例２の軟磁性フィルム（平均厚み１５０μｍ）を製造した。 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 μm) of Example 2 was produced in the same manner as Example 1 except that the soft magnetic resin composition was used.
　　比較例１～３
　表１に記載の材料および配合割合で、軟磁性樹脂組成物を得た。この軟磁性樹脂組成物を用いた以外は、実施例１と同様にして、比較例の軟磁性フィルムを製造した。 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.
　（引張貯蔵弾性率Ｅ´１６０）
　各実施例および各比較例において、軟磁性樹脂組成物を除いた軟磁性除外成分（エポキシ樹脂、フェノール樹脂、アクリル樹脂、熱硬化性触媒、および、レオロジーコントロール剤）を混合し、軟磁性除外組成物を得た。各実施例および各比較例の軟磁性フィルムの製造と同様にして、この軟磁性除外組成物をメチルエチルケトンに溶解させて軟磁性除外組成物溶液を調製し、セパレータ上に塗布および乾燥させ、半硬化状態のフィルムを製造した後、加熱硬化させることにより、軟磁性除外成分からなるフィルム（完全硬化状態）を作製した。 (Tensile storage modulus E ′ 160 )
In each example and each comparative example, a soft magnetic exclusion composition (epoxy resin, phenol resin, acrylic resin, thermosetting catalyst, and rheology control agent) excluding the soft magnetic resin composition was mixed, and the soft magnetic exclusion composition was mixed. I got a thing. In the same manner as in the production of the soft magnetic film of each example and each comparative example, this soft magnetic exclusion composition was dissolved in methyl ethyl ketone to prepare a soft magnetic exclusion composition solution, which was applied and dried on a separator, and semi-cured. After producing the film in a state, it was cured by heating to produce a film (completely cured state) composed of the soft magnetic exclusion component.
　このフィルムについて、下記の条件に基づいて、動的粘弾性測定を実施し、１６０℃における引張貯蔵弾性率Ｅ´１６０を求めた。 About this film, dynamic viscoelasticity measurement was implemented based on the following conditions, and the tensile storage elastic modulus E ′ 160 at 160 ° C. was obtained.
　動的粘弾性測定装置（ＭＤＡ）：商品名「ＲＳＡＩＩＩ」、レオメトリックサイエンティフィック社製
　モード：引張モード
　昇温速度：１０℃／分
　周波数：１Ｈｚ
　サンプル厚み：４０～１３０μｍ
　チャック間距離：２０ｍｍ
　ひずみ：０．１％　　
　測定温度範囲：０℃～２００℃
　この結果を表１に示す。 Dynamic viscoelasticity measuring apparatus (MDA): trade name “RSAIII”, manufactured by Rheometric Scientific Inc. Mode: Tensile mode Temperature rising rate: 10 ° C./min Frequency: 1 Hz
Sample thickness: 40-130 μm
Distance between chucks: 20mm
Strain: 0.1%
Measurement temperature range: 0 ° C to 200 ° C
The results are shown in Table 1.
　（空隙率）
　各実施例および各比較例の軟磁性フィルムの比重（Ｓ．Ｇ．）を、電子分析天秤（島津製作所社製、「ＡＥＬ－２００」）を用いて、比重測定法により、空気中の軟磁性フィルムでの重さＷ１（ｇ）と、水中での軟磁性フィルムＷ２の重さ（ｇ）とをそれぞれ測定し、下記式により算出した。 (Porosity)
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. 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.
　　比重（Ｓ．Ｇ．）＝Ｗ１／（Ｗ１－Ｗ２）
　次いで、軟磁性フィルムの空隙率を、下記式に従い測定した。 Specific gravity (SG) = W1 / (W1-W2)
Next, the porosity of the soft magnetic film was measured according to the following formula.
　空隙率（％）＝｛１－（比重（Ｓ．Ｇ．））／（理論比重）｝×１００
　この結果を表１に示す。 Porosity (%) = {1− (specific gravity (SG)) / (theoretical specific gravity)} × 100
The results are shown in Table 1.
　（耐リフロー性）
　各実施例および各比較例の軟磁性フィルムを回路基板の一方面に、アクリル系接着剤を介して積層し、軟磁性フィルム積層基板を作製した（図１参照）。この軟磁性フィルム積層基板を、ＩＲリフロー炉内部に２６０℃１０秒間の条件にて通過させることにより、リフロー工程を実施した。 (Reflow resistance)
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.
　このリフロー工程後の軟磁性フィルム積層回路基板を目視した。軟磁性フィルムの外観に変化が確認されなかった場合を○、軟磁性フィルムに膨れや剥離などの外観不良が確認された場合を×と評価した。
この結果を表１に示す。 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.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　表における各成分中の数値は、固形分を示す。各実施例および表中の各成分の略称について、以下にその詳細を記載する。
・Ｆｅ－Ｓｉ－Ａｌ合金：商品名「ＦＭＥ３ＤＨ」、軟磁性粒子、扁平状、平均粒子径４３μｍ、平均厚み１μｍ、比重６．８、山陽特殊製鋼社製
・トリスヒドロキシフェニルメタン型エポキシ樹脂：商品名「ＥＰＰＮ－５０１ＨＹ」、上記一般式（１）のエポキシ樹脂、エポキシ当量１６９ｇ／ｅｑ．、ＩＣＩ粘度(１５０℃)０．１Ｐａ・ｓ、比重１．２５、日本化薬社製
・クレゾールノボラック型樹脂：商品名「ＫＩ－３０００－４」、エポキシ当量１９９ｇ／ｅｑ．、ＩＣＩ粘度(１５０℃)０．４Ｐａ・ｓ、比重１．２１、東都化成社製
・ビスフェノールＡ型エポキシ樹脂：商品名「エピコートＹＬ９８０」、エポキシ当量１８０ｇ／ｅｑ．、ＩＣＩ粘度(１５０℃)０．０５Ｐａ・ｓ、比重１．１５、三菱化学社製
・フェノールノボラック樹脂：商品名「レヂトップＬＶＲ８２１０ＤＬ」、水酸基当量１０４ｇ／ｅｑ．、ＩＣＩ粘度(１５０℃)０．０３Ｐａ・ｓ、比重１．２、群栄化学工業社製
・フェノールビフェニレン樹脂：商品名「ＭＥＨ－７８５１ＳＳ」、水酸基当量２０３ｇ／ｅｑ．、ＩＣＩ粘度(１５０℃)０．０５Ｐａ・ｓ、比重１．１８、明和化成社製
・ＳＧ-Ｐ３：アクリル酸エステル系共重合体溶液、商品名「テイサンレジン ＳＧ－Ｐ３」、エポキシ基含有のアクリル酸エチル－アクリル酸ブチル－アクリロニトリル共重合体、比重０．８５、重量平均分子量８５０，０００、エポキシ価２１０ｅｑ．／ｇ、ガラス転移温度１２℃、ゴム含有割合１５質量％、溶媒：メチルエチルケトン、ナガセケムテックス社製
・ＳＧ－７０Ｌ：アクリル酸エステル系共重合体溶液、商品名「テイサンレジン ＳＧ－７０Ｌ」、カルボキシ基およびヒドロキシ基含有のアクリル酸エチル－アクリル酸ブチル－アクリロニトリル共重合体、比重１．００、重量平均分子量９００，０００、ガラス転移温度－１３℃、ゴム含有割合１２．５質量％、溶媒：メチルエチルケトンおよびトルエンの混合液、ナガセケムテックス社製
・２ＰＨＺ－ＰＷ：熱硬化触媒、２－フェニル－１Ｈ－イミダゾール４，５－ジメタノール、比重１．３３、商品名「キュアゾール２ＰＨＺ－ＰＷ」、四国化成社製
・ＢＹＫ４３０：商品名、レオロジーコントロール剤、ウレア変性中極性ポリアマイド、比重０．８６、固形分３０質量％、イソブチルアルコールおよびソルベントナフサの混合液、ビックケミージャパン社製 The numerical value in each component in the table indicates the solid content. Details of the abbreviations of each component in each example and table are described below.
-Fe-Si-Al alloy: trade name "FME3DH", soft magnetic particles, flat, average particle size 43μm, average thickness 1μm, specific gravity 6.8, manufactured by Sanyo Special Steel Co., Ltd. • Trishydroxyphenylmethane type epoxy resin: Product Name “EPPN-501HY”, epoxy resin of general formula (1), epoxy equivalent 169 g / eq. ICI viscosity (150 ° C.) 0.1 Pa · s, specific gravity 1.25, Nippon Kayaku Co., Ltd., cresol novolac type resin: trade name “KI-3000-4”, epoxy equivalent 199 g / eq. , ICI viscosity (150 ° C.) 0.4 Pa · s, specific gravity 1.21, manufactured by Toto Kasei Co., Ltd., bisphenol A type epoxy resin: trade name “Epicoat YL980”, epoxy equivalent 180 g / eq. ICI viscosity (150 ° C.) 0.05 Pa · s, specific gravity 1.15, manufactured by Mitsubishi Chemical Co., Ltd., phenol novolac resin: trade name “Resitop LVR8210DL”, hydroxyl group equivalent 104 g / eq. ICI viscosity (150 ° C.) 0.03 Pa · s, specific gravity 1.2, manufactured by Gunei Chemical Industry Co., Ltd., phenol biphenylene resin: trade name “MEH-7851SS”, hydroxyl group equivalent 203 g / eq. , ICI viscosity (150 ° C.) 0.05 Pa · s, specific gravity 1.18, manufactured by Meiwa Kasei Co., Ltd. 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. / G, glass transition temperature 12 ° C., rubber content 15% by mass, solvent: methyl ethyl ketone, manufactured by Nagase ChemteX Corporation, SG-70L: acrylate copolymer solution, trade name “Taisan Resin SG-70L”, carboxy And hydroxy group-containing ethyl acrylate-butyl acrylate-acrylonitrile copolymer, specific gravity 1.00, weight average molecular weight 900,000, glass transition temperature -13 ° C., rubber content 12.5% by mass, solvent: methyl ethyl ketone And toluene mixed solution, manufactured by Nagase ChemteX Corp., 2PHZ-PW: thermosetting catalyst, 2-phenyl-1H-imidazole 4,5-dimethanol, specific gravity 1.33, trade name “CURESOL 2PHZ-PW”, Shikoku Chemicals BYK430: Product name, rheology control agent, urea-modified medium polarity Polyamide, specific gravity 0.86, solid content 30% by mass, mixed solution of isobutyl alcohol and solvent naphtha, manufactured by Big Chemie Japan
　なお、上記発明は、本発明の例示の実施形態として提供したが、これは単なる例示に過ぎず、限定的に解釈してはならない。当該技術分野の当業者によって明らかな本発明の変形例は、後記特許請求の範囲に含まれる。 Although the above invention has been provided as an exemplary embodiment of the present invention, this is merely an example and should not be interpreted in a limited manner. Variations of the present invention that are apparent to one of ordinary skill in the art are within the scope of the following claims.
　本発明の軟磁性フィルムは、各種の工業製品に適用することができ、例えば、スマートフォン、タブレット型パソコン、位置検出装置などに好適に用いることができる。 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.
４　軟磁性フィルム
７　軟磁性粒子 4 Soft magnetic film 7 Soft magnetic particles

Claims (4)

  1. 　軟磁性樹脂組成物から形成される軟磁性フィルムであって、
    　前記軟磁性樹脂組成物が、扁平状の軟磁性粒子および樹脂成分を含有し、
    　前記軟磁性樹脂組成物に対する前記軟磁性粒子の体積割合が、固形分換算で、６５体積％以上であり、
    　前記軟磁性フィルムの空隙率が、２．５体積％以下であることを特徴とする、軟磁性フィルム。     A soft magnetic film formed from a soft magnetic resin composition,
    The soft magnetic resin composition contains flat soft magnetic particles and a resin component,
    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,
    A soft magnetic film, wherein the soft magnetic film has a porosity of 2.5% by volume or less.
  2. 　前記樹脂成分が、多官能モノマー型エポキシ樹脂、フェノール樹脂およびアクリル樹脂を含有し、
    　前記樹脂成分に対する前記アクリル樹脂の体積割合が、１０体積％以下であることを特徴とする、請求項１に記載の軟磁性フィルム。     The resin component contains a polyfunctional monomer type epoxy resin, a phenol resin and an acrylic resin,
    The soft magnetic film according to claim 1, wherein a volume ratio of the acrylic resin to the resin component is 10% by volume or less.
  3. 　前記アクリル樹脂のガラス転移温度が、０℃以上であることを特徴とする、請求項２に記載の軟磁性フィルム。 The soft magnetic film according to claim 2, wherein the glass transition temperature of the acrylic resin is 0 ° C or higher.
  4. 　前記軟磁性樹脂組成物から前記軟磁性粒子を除外した軟磁性粒子除外成分の動的粘弾性測定における昇温速度１０℃／分、周波数１Ｈｚでの１６０℃の引張貯蔵弾性率Ｅ´が、５．５×１０８Ｐａ以上であることを特徴とする、請求項１に記載の軟磁性フィルム。 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 5 The soft magnetic film according to claim 1, wherein the soft magnetic film is 5 × 10 8 Pa or more.
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WO2014132701A1 (en) * 2013-02-26 2014-09-04 日東電工株式会社 Soft magnetic thermosetting adhesive film, soft magnetic film-laminated circuit board, and position-detecting device

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