WO2014132879A1 - Soft magnetic thermosetting film and soft magnetic film - Google Patents

Soft magnetic thermosetting film and soft magnetic film Download PDF

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Publication number
WO2014132879A1
WO2014132879A1 PCT/JP2014/054105 JP2014054105W WO2014132879A1 WO 2014132879 A1 WO2014132879 A1 WO 2014132879A1 JP 2014054105 W JP2014054105 W JP 2014054105W WO 2014132879 A1 WO2014132879 A1 WO 2014132879A1
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WO
WIPO (PCT)
Prior art keywords
soft magnetic
film
mass
resin
thermosetting
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PCT/JP2014/054105
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French (fr)
Japanese (ja)
Inventor
剛志 土生
将太郎 増田
亮人 松富
Original Assignee
日東電工株式会社
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Filing date
Publication date
Priority claimed from JP2013035700A external-priority patent/JP6297260B2/en
Priority claimed from JP2013243065A external-priority patent/JP6297314B2/en
Application filed by 日東電工株式会社 filed Critical 日東電工株式会社
Priority to EP14757682.1A priority Critical patent/EP2963658A4/en
Publication of WO2014132879A1 publication Critical patent/WO2014132879A1/en

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
    • H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
    • H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
    • H01F1/12—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials
    • H01F1/14—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials metals or alloys
    • H01F1/20—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials metals or alloys in the form of particles, e.g. powder
    • H01F1/22—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials metals or alloys in the form of particles, e.g. powder pressed, sintered, or bound together
    • H01F1/24—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials metals or alloys in the form of particles, e.g. powder pressed, sintered, or bound together the particles being insulated
    • H01F1/26—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials metals or alloys in the form of particles, e.g. powder pressed, sintered, or bound together the particles being insulated by macromolecular organic substances
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F41/00—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties
    • H01F41/14—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for applying magnetic films to substrates
    • H01F41/16—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for applying magnetic films to substrates the magnetic material being applied in the form of particles, e.g. by serigraphy, to form thick magnetic films or precursors therefor

Definitions

  • the present invention relates to a soft magnetic thermosetting film and a soft magnetic film obtained therefrom.
  • 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 contains a soft magnetic material on the surface (opposite 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 a soft magnetic film 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.
  • a soft magnetic film is generally manufactured by heat-curing a thermosetting resin containing soft magnetic powder and a binder resin.
  • the soft magnetic film is stored for a long time in a high temperature and high humidity atmosphere after heating, there arises a problem that magnetic properties such as relative permeability deteriorate.
  • An object of the present invention is to provide a soft magnetic thermosetting film in which deterioration of magnetic properties is suppressed even after being stored for a long time in a high temperature and high humidity atmosphere, and a soft magnetic film obtained therefrom.
  • the soft magnetic thermosetting film of the present invention is a soft magnetic thermosetting film containing soft magnetic particles, and has an initial relative magnetic permeability ⁇ 0 ′ at a frequency of 1 MHz immediately after the soft magnetic thermosetting film is heated and cured.
  • the ratio ( ⁇ 1 ′ / ⁇ 0 ′) of the relative magnetic permeability ⁇ 1 ′ at a frequency of 1 MHz when the soft magnetic thermosetting film was cured by heating and allowed to stand for 168 hours in an atmosphere of 85 ° C. and 85% RH was 0. It is characterized by being 85 or more.
  • the soft magnetic thermosetting film of the present invention is preferably formed from a soft magnetic thermosetting composition containing 40% by volume or more of the soft magnetic particles.
  • the soft magnetic thermosetting composition contains an epoxy resin, a phenol resin, and an acrylic resin.
  • the soft magnetic film of the present invention is characterized by being obtained by heating and curing the above-mentioned soft magnetic thermosetting film.
  • the soft magnetic film of the present invention obtained by heating and curing the soft magnetic thermosetting film of the present invention is excellent in that the deterioration of magnetic properties is suppressed even after storage (standing) for a long time in a high temperature and high humidity atmosphere. With magnetic properties.
  • the soft magnetic thermosetting film of the present invention is formed from, for example, a soft magnetic thermosetting 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
  • Fe—Si—Al alloys having a Si content of 9 to 15% by mass are more preferable. Thereby, the magnetic characteristics of the soft magnetic film can be improved.
  • the shape of the soft magnetic particles is preferably a flat shape (plate shape).
  • the flatness (flatness) is, for example, 8 or more, preferably 15 or more, and for example, 80 or less, preferably 65 or less.
  • the aspect ratio is calculated as an aspect ratio obtained by dividing the particle diameter of 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.
  • 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 mass ratio of the soft magnetic particles in the soft magnetic thermosetting composition is, for example, 70% by mass or more, preferably 80% by mass or more, and more preferably 85%. For example, it is 95% by mass or less, preferably 92% by mass or less, and more preferably 90% by mass or less.
  • the volume ratio of the soft magnetic particles in the soft magnetic thermosetting composition is, for example, 30% by volume or more, preferably 40% by volume or more, more preferably 50% by volume or more, and for example, 80% by volume or less. Preferably, it is 70 volume% or less, More preferably, it is 60 volume% or less.
  • the resin component contains a thermosetting resin.
  • thermosetting resin examples include epoxy resins, phenol resins, amino resins, unsaturated polyester resins, polyurethane resins, silicone resins, urea resins, melamine resins, thermosetting polyimide resins, diallyl phthalate resins, and the like.
  • an epoxy resin and a phenol resin are mentioned, More preferably, combined use of an epoxy resin and a phenol resin is mentioned. These can be used alone or in combination of two or more.
  • the epoxy resin is not limited as long as it is generally used as an adhesive composition.
  • bisphenol type epoxy resin particularly, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, brominated bisphenol.
  • a hydantoin type epoxy resin a trisglycidyl isocyanurate type epoxy resin, a glycidylamine type epoxy resin and the like can be mentioned. These can be used alone or in combination of two or more.
  • epoxy resins preferably, bisphenol type epoxy resin, novolac type epoxy resin, orthocresol novolac type epoxy resin, biphenyl type epoxy resin, trishydroxyphenylmethane type resin, tetraphenylolethane type epoxy resin are mentioned, More preferably, a bisphenol type epoxy resin is mentioned.
  • the reactivity with the phenol resin is excellent, and as a result, in the soft magnetic film obtained by heating and curing the soft magnetic thermosetting film, the magnetic properties in a high temperature and high humidity atmosphere are improved. Excellent long-term storage.
  • the phenol resin is a curing agent for an epoxy resin.
  • a novolak resin is preferable, a phenol novolac resin, a phenol aralkyl resin, and more preferably a phenol aralkyl resin.
  • the content ratio is, for example, 15 parts by mass or more, preferably 30 parts by mass or more, and for example, 70 parts by mass or less, preferably 50 parts by mass or less, more preferably 40 parts by mass or less.
  • the content rate of the phenol resin with respect to 100 mass parts of components is 5 mass parts or more, for example, Preferably, it is 15 mass parts or more, for example, is 30 mass parts or less, Preferably, it is 20 mass parts or less.
  • the content of the epoxy resin with respect to 100 parts by mass of the resin component is, for example, 10 parts by mass or more, 25 parts by mass or more, for example, 50 parts by mass or less, and the content ratio of the phenol resin to 100 parts by mass of the resin component is, for example, 10 parts by mass or more, preferably 25 parts by mass or more. For example, it is 50 parts by mass or less.
  • the content of the epoxy resin with respect to 100 parts by mass of the resin component is, for example, 5 parts by mass or more, 15 parts by mass or more, for example, 30 parts by mass or less, and the content ratio of the phenol resin to 100 parts by mass of the resin component is, for example, 15 parts by mass or more, preferably 35 parts by mass or more. For example, it is 70 parts by mass or less.
  • the epoxy equivalent when two types of epoxy resins are used in combination is the epoxy equivalent of all epoxy resins obtained by multiplying the epoxy equivalent of each epoxy resin by the mass ratio of each epoxy resin to the total amount of epoxy resin, and adding them together. is there.
  • the hydroxyl group equivalent in the phenol resin is, for example, 0.2 equivalents or more, preferably 0.5 equivalents or more, and preferably, 2.0 equivalents or less, preferably 1 equivalent or less, per equivalent of epoxy group of the epoxy resin. 1.2 equivalents or less.
  • the amount of the hydroxyl group is within the above range, the curing reaction of the soft magnetic thermosetting film becomes good, and deterioration can be suppressed.
  • the resin component preferably contains an acrylic resin in addition to the thermosetting resin. More preferably, an acrylic resin, an epoxy resin, and a phenol resin are used in combination. More preferably, the resin component consists only of an epoxy resin, a phenol resin, and an acrylic resin. When the resin component contains these resins, a plurality of soft magnetic thermosetting films are laminated and hot pressed to produce a single soft magnetic film, which is uniform and uniform at the lamination interface. A soft magnetic film with good magnetic properties can be obtained.
  • 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, octyl, isooctyl, nonyl, isononyl, decyl, isodecyl, undecyl, lauryl, tridecyl, tetradecyl, stearyl, octadecyl, dodecyl 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 monomers such as (
  • a glycidyl group-containing monomer, a carboxyl group-containing monomer, or a hydroxyl group-containing monomer is used.
  • the acrylic resin is a copolymer of (meth) acrylic acid alkyl ester and these other monomers, that is, when the acrylic resin has a glycidyl group, a carboxyl group or a hydroxyl group, the reflow resistance of the soft magnetic film is Even better.
  • the blending ratio (mass) of the other monomer is preferably 40% by mass or less with respect to the copolymer.
  • 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. By setting it as this range, it is excellent in the adhesiveness and reflow resistance of a soft-magnetic thermosetting film.
  • a weight average molecular weight is measured by a standard polystyrene conversion value by gel permeation chromatography (GPC).
  • the glass transition point (Tg) of the acrylic resin is, for example, ⁇ 30 ° C. or more, preferably ⁇ 20 ° C. or more, and for example, 30 ° C. or less, preferably 15 ° C. or less. It is excellent in the adhesiveness of a soft-magnetic thermosetting film as it is more than the said minimum. On the other hand, it is excellent in the handleability of a soft-magnetic thermosetting film as it is below the said upper limit.
  • the glass transition point is obtained from the maximum value of the loss tangent (tan ⁇ ) measured using a dynamic viscoelasticity measuring device (DMA, frequency 1 Hz, heating rate 10 ° C./min).
  • the content ratio of the thermosetting resin in the resin component is, for example, 35% by mass or more, preferably more than 50% by mass, and more preferably 52% by mass or more. For example, it is 90 mass% or less, Preferably, it is 80 mass% or less, More preferably, it is 60 mass% or less.
  • the content ratio of the thermosetting resin is within the above range, particularly when the thermosetting resin is rich (over 50% by mass), it is effective for the expansion of the resin due to water absorption or heat, and hence the generation of voids in the soft magnetic film. Therefore, long-term storage stability of magnetic properties in a high-temperature and high-humidity atmosphere is excellent.
  • the content ratio of the acrylic resin in the resin component is, for example, 10% by mass or more, preferably 20% by mass or more, more preferably 40% by mass or more, and for example, 65% by mass or less, preferably 50% by mass. %, More preferably 48% by mass or less.
  • the content ratio of the resin component in the soft magnetic thermosetting composition is, for example, 5% by mass or more, preferably 8% by mass or more, more preferably 10% by mass or more, and for example, 30% by mass or less. Preferably, it is 20 mass% or less, More preferably, it is 15 mass% or less. By setting it within the above range, the soft magnetic film is excellent in film formability and magnetic properties.
  • the content of the thermosetting resin is 100 mass parts of the soft magnetic particle excluded component obtained by removing the soft magnetic particles from the soft magnetic thermosetting composition.
  • the soft magnetic particle excluded component obtained by removing the soft magnetic particles from the soft magnetic thermosetting composition.
  • it is 99 parts by mass or less, preferably 90 parts by mass or less, more preferably 80 parts by mass or less, still more preferably 70 parts by mass or less, and most preferably 60 parts by mass or less.
  • the soft magnetic particle exclusion component is a component composed of a resin component, a thermosetting catalyst (described later) and an additive (described later) that are added as necessary, and the soft magnetic particles and the solvent include Not included.
  • the resin component can also contain other thermoplastic resins other than thermosetting resins and acrylic resins.
  • thermoplastic resins examples include natural rubber, butyl rubber, isoprene rubber, chloroprene rubber, ethylene-vinyl acetate copolymer, copolymer, polybutadiene resin, polycarbonate resin, thermoplastic polyimide resin, polyamide resin (6- Nylon, 6,6-nylon, etc.), phenoxy resin, saturated polyester resin (PET, PBT, etc.), polyamideimide resin, fluororesin and the like. These resins can be used alone or in combination of two or more.
  • the soft magnetic thermosetting composition preferably contains a thermosetting catalyst.
  • thermosetting catalyst is not limited as long as it is a catalyst that accelerates the curing of the resin component by heating.
  • a salt having an imidazole skeleton, a salt having a triphenylphosphine structure, a salt having a triphenylborane structure, amino And group-containing compounds is used.
  • Examples of the salt having an imidazole skeleton include 2-phenylimidazole (trade name; 2PZ), 2-ethyl-4-methylimidazole (trade name; 2E4MZ), 2-methylimidazole (trade name; 2MZ), 2-un Decylimidazole (trade name; C11Z), 2-phenyl-4,5-dihydroxymethylimidazole (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.).
  • a thermosetting catalyst can be used individually or can be used together 2 or more types.
  • thermosetting catalyst examples include a spherical shape and an ellipsoidal shape.
  • the blending ratio of the thermosetting catalyst is, for example, 0.1 parts by mass or more, preferably 0.3 parts by mass or more, 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 thermosetting film can be cured by heating at a low temperature and in a short time, and the magnetic properties can be stored for a long time in a high temperature and high humidity atmosphere. Excellent reflow resistance.
  • the soft magnetic thermosetting composition (and thus the soft magnetic thermosetting film and the soft magnetic film) may contain a commercially available or known additive such as a dispersant, a crosslinking agent, and an inorganic filler, if necessary. it can.
  • a commercially available or known additive such as a dispersant, a crosslinking agent, and an inorganic filler, if necessary. it can.
  • the soft magnetic thermosetting composition preferably contains a dispersant.
  • the dispersant examples include polyether phosphate esters, silane coupling agents, and titanate coupling agents.
  • polyether phosphate ester is mentioned.
  • the soft magnetic thermosetting composition contains a dispersant, particularly a polyether phosphate, the coating property of the soft magnetic thermosetting composition is improved and the magnetic properties of the soft magnetic film are further improved. be able to.
  • polyether phosphate esters examples include polyoxyalkylene alkyl ether phosphate esters and polyoxyalkylene alkyl phenyl ether phosphate esters.
  • polyoxyalkylene alkyl ether phosphate ester is used.
  • the polyoxyalkylene alkyl ether phosphate ester has a form in which 1 to 3 alkyl-oxy-poly (alkyleneoxy) groups are bonded to the phosphorus atom of the phosphate.
  • alkyl-oxy-poly (alkyleneoxy) group ie, a polyoxyalkylene alkyl ether moiety
  • the number of repeating alkyleneoxy with respect to the poly (alkyleneoxy) moiety is not particularly limited. It can be appropriately selected from the range of (preferably 3 to 20).
  • the alkylene at the poly (alkyleneoxy) moiety is preferably an alkylene group having 2 to 4 carbon atoms.
  • alkyl group is not particularly limited, and for example, an alkyl group having 6 to 30 carbon atoms is preferable, and an alkyl group having 8 to 20 carbon atoms is more preferable.
  • examples of the alkyl group include a decyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, and an octadecyl group.
  • the polyoxyalkylene alkyl ether phosphate ester has a plurality of alkyl-oxy-poly (alkyleneoxy) groups, the plurality of alkyl groups may be different or the same.
  • the polyether phosphate ester may be a mixture with an amine or the like.
  • the acid value of the polyether phosphate ester is, for example, 10 or more, preferably 15 or more, and for example, 200 or less, preferably 150 or less.
  • the acid value is measured by a neutralization titration method or the like.
  • silane coupling agent examples include 3-methacryloxypropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and the like.
  • Dispersants can be used alone or in combination of two or more.
  • dispersant examples include HIPLAAD series ("ED152”, “ED153”, “ED154”, “ED118”, “ED174”, “ED251”) from Enomoto Kasei Co., Ltd., KBM series ("KBM303”) from Shin-Etsu Chemical Co., Ltd. , “KBM503”).
  • the content ratio of the dispersant is, for example, 0.1 parts by mass or more, preferably 0.2 parts by mass or more with respect to 100 parts by mass of the soft magnetic particles. For example, it is 5 mass parts or less, Preferably, it is 2 mass parts or less.
  • the soft magnetic thermosetting composition can be prepared by mixing the above components in the above content ratio.
  • a soft magnetic thermosetting composition solution in which the above-described soft magnetic thermosetting composition is dissolved or dispersed in a solvent 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 thermosetting 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 thermosetting composition solution is applied to the surface of a release substrate (separator, core material, etc.) and dried. Thereby, a soft magnetic thermosetting film is obtained.
  • 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
  • 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 thereof include a resin substrate reinforced with a woven fiber, a silicon substrate, a glass substrate, 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 soft magnetic thermosetting film is a soft magnetic thermosetting adhesive film that is in a semi-cured state (B stage state) at room temperature (specifically, 25 ° C.) and has good adhesiveness.
  • the soft magnetic thermosetting film preferably contains flat soft magnetic particles, and the flat soft magnetic particles are arranged in the two-dimensional in-plane direction of the soft magnetic thermosetting 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 thermosetting film.
  • the soft magnetic thermosetting film is filled with soft magnetic particles at a high ratio and has excellent magnetic properties. Moreover, thinning is achieved.
  • 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 film of the present invention has, for example, a single-layer structure composed of only a single layer of a soft magnetic thermosetting film, a multilayer structure in which a soft magnetic thermosetting film is laminated on one or both sides of a core material, A multi-layer structure in which separators are laminated on one side or both sides of a magnetic thermosetting film can be used.
  • the soft magnetic film is formed from the above soft magnetic thermosetting film. Specifically, the soft magnetic film can be obtained by heat curing the soft magnetic thermosetting film.
  • a plurality of 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 soft magnetic thermosetting film can be filled with soft magnetic particles at a high rate, and the magnetic properties can be improved.
  • 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 in a semi-cured state is cured by heating, and a soft magnetic film in a cured state (C stage state) is obtained.
  • 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 relative permeability (initial relative permeability ⁇ 0 ′) at a frequency of 1 MHz immediately after being heat-cured is, for example, 100 or more, preferably 150 or more, more preferably 180 or more, and for example, 400 or less.
  • the relative permeability (relative permeability ⁇ 1 ′) at a frequency of 1 MHz when left in an atmosphere of 85 ° C. and 85% RH for 168 hours is, for example, 100 or more, preferably 150 or more, more preferably 180 or more, for example, 400 or less.
  • the ratio ( ⁇ 1 ′ / ⁇ 0 ′) between the initial relative permeability ⁇ 0 ′ and the relative permeability ⁇ 1 ′ is 0.85 or more, preferably 0.90 or more, more preferably 0.95 or more, and still more preferably Is 0.96 or more, most preferably 0.97 or more, and for example, 1.00 or less.
  • the soft magnetic film is excellent in long-term storage stability of magnetic properties in a high temperature and high humidity atmosphere.
  • the relative magnetic permeability ( ⁇ 0 ′ and ⁇ 1 ′) is measured by an one-turn method (frequency 1 MHz) using an impedance analyzer (manufactured by Agilent, “4294A”).
  • the soft magnetic particles contained in the soft magnetic film are 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. For this reason, the soft magnetic film is a thin film and has excellent relative magnetic permeability.
  • 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. .
  • This soft magnetic film can be suitably used as, for example, an antenna, a coil, or a soft magnetic film (magnetic film) to be laminated on a circuit board on which these are formed. More specifically, it can be used for applications such as smartphones, personal computers, and position detection devices.
  • a method of fixing the soft magnetic film to the circuit board through an adhesive layer, a soft magnetic thermosetting film directly attached to the circuit board examples thereof include a method in which a curable film is cured by heating to form a soft magnetic film and fixed to a circuit board.
  • a method in which a soft magnetic thermosetting film is directly attached to a circuit board and then the soft magnetic thermosetting film is cured by heating is preferable. It is done.
  • a method of fixing the soft magnetic film to the circuit board through an adhesive layer is preferable.
  • the adhesive layer a known one that is usually used as an adhesive layer of a circuit board is used. For example, by applying and drying an adhesive such as an epoxy adhesive, a polyimide adhesive, or an acrylic adhesive It is formed.
  • the thickness of the adhesive layer is, for example, 10 to 100 ⁇ m.
  • the soft magnetic thermosetting film since the ratio ( ⁇ 1 ′ / ⁇ 0 ′) between the initial relative permeability ⁇ 0 ′ and the relative permeability ⁇ 1 ′ is 0.85 or more, the soft magnetic thermosetting film Even when a soft magnetic film obtained by heat curing is stored in a high temperature and high humidity atmosphere for a long time, deterioration of the relative magnetic permeability of the soft magnetic film can be suppressed. Thereby, excellent magnetic properties can be exhibited for a long time.
  • Resistance temperature in a high temperature and high humidity atmosphere is, for example, 50 ° C. or higher, preferably 80 ° C. or higher, and for example, 150 ° C. or lower, preferably 100 ° C. or lower.
  • Resistance humidity in a high temperature and high humidity atmosphere is, for example, 50% RH or more, preferably 80% RH or more, and, for example, 100% RH or less, preferably 90% RH or less.
  • the storable time in a high temperature and high humidity atmosphere is, for example, 96 hours or more, preferably 168 hours or more, more preferably 400 hours or more, and further preferably 700 hours or more.
  • Example 1 Soft magnetic thermosetting film
  • Soft magnetic particles 500 parts by mass, acrylic ester polymer 22 parts by mass, bisphenol A type epoxy resin (“Epicoat 1004”) 45 parts by mass so that the soft magnetic particles are 40% by volume with respect to the soft magnetic thermosetting composition.
  • This soft magnetic thermosetting composition was dissolved in methyl ethyl ketone to prepare a soft magnetic thermosetting composition solution having a solid content of 43% by mass.
  • This soft magnetic thermosetting composition solution was applied onto a separator (average thickness: 50 ⁇ m) made of a polyethylene terephthalate film subjected to silicone release treatment, and then dried at 130 ° C. for 2 minutes.
  • a soft magnetic thermosetting film (average thickness of only the soft magnetic thermosetting film, 90 ⁇ m) on which the separator was laminated was manufactured.
  • Soft magnetic film Next, four layers of this soft magnetic thermosetting film were laminated and heated and cured by hot pressing under the conditions of 175 ° C., 30 minutes, and 20 MPa to produce a soft magnetic film.
  • Examples 2-4 Soft magnetic thermosetting compositions were obtained with the materials and blending ratios shown in Table 1. Soft magnetic thermosetting films and thermosetting films of Examples 2 to 4 were produced in the same manner as in Example 1 except that this soft magnetic thermosetting composition was used.
  • Comparative Example 1 (Soft magnetic thermosetting film) By mixing 500 parts by weight of soft magnetic particles and 106 parts by weight of ethylene vinyl acetate copolymer so that the soft magnetic particles are 40% by volume with respect to the soft magnetic thermosetting composition, the soft magnetic thermosetting composition is mixed. Got.
  • This soft magnetic thermosetting composition was dissolved in toluene to prepare a soft magnetic thermosetting composition solution having a solid concentration of 40% by mass.
  • This soft magnetic thermosetting composition solution was applied onto a separator (average thickness: 50 ⁇ m) made of a polyethylene terephthalate film subjected to silicone release treatment, and then dried at 130 ° C. for 2 minutes.
  • a soft magnetic thermosetting film (average thickness of only the soft magnetic thermosetting film, 90 ⁇ m) on which the separator was laminated was manufactured.
  • Soft magnetic film Next, four layers of this soft magnetic thermosetting film were laminated and heat-cured by hot pressing under the conditions of 175 ° C., 30 minutes, 20 MPa, to produce the soft magnetic film of Comparative Example 1.
  • Comparative Examples 2 and 3 Soft magnetic thermosetting compositions were obtained with the materials and blending ratios shown in Table 1. A soft magnetic thermosetting film and a soft magnetic film of Comparative Examples 2 and 3 were produced in the same manner as in Example 1 except that this soft magnetic thermosetting composition was used.
  • the soft magnetic films of Examples 1 to 4 have a high ratio of the ratio based on the initial relative permeability at the time when the soft magnetic film was produced even after 400 hours or 700 hours.
  • the magnetic permeability was provided, that is, the decrease in the relative magnetic permeability was suppressed.
  • the soft magnetic films of Comparative Examples 1 to 3 after 400 hours or 700 hours, the relative magnetic permeability was greatly reduced with reference to the initial relative magnetic permeability at the time of producing the soft magnetic film. Further, in the soft magnetic films of Comparative Example 2 and Comparative Example 3, the decrease in the relative magnetic permeability proceeded in 400 to 700 hours.
  • Phenol aralkyl resin Trade name “Mirex XLC-4L”, hydroxyl equivalent 1 0 g / eq, Mitsui Chemicals Co., Ltd. 2-Phenyl-4,5-dihydroxymethylimidazole: thermosetting catalyst, trade name “Curazole 2PHZ-PW”, Shikoku Kasei Co., Ltd., polyether phosphate ester: dispersant, trade name “HIPLAAD ED152”, manufactured by Enomoto Kasei Co., Ltd., acid value 20 -Ethylene vinyl acetate copolymer: trade name "EV170", manufactured by Mitsui DuPont Polychemical Co., Ltd.
  • the above invention is provided as an exemplary embodiment of the present invention, this is merely an example and is limitedly interpreted. should not be done. Variations of the present invention that are apparent to one of ordinary skill in the art are within the scope of the following claims.
  • the soft magnetic thermosetting film and soft magnetic film of the present invention can be applied to various industrial products, and can be used, for example, for position detection devices such as digitizers.

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Abstract

The soft magnetic thermosetting film according to the present invention contains soft magnetic particles. The ratio (µ1'/µ0') of the initial relative permeability µ0' of the soft magnetic thermosetting film at a frequency of 1 MHz immediately after thermal curing thereof and the relative permeability µ1' at a frequency of 1 MHz when the soft magnetic thermosetting film has been left for 168 hours in an 85°C, 85% RH atmosphere is at least 0.85.

Description

軟磁性熱硬化性フィルム、および、軟磁性フィルムSoft magnetic thermosetting film and soft magnetic film
　本発明は、軟磁性熱硬化性フィルムおよびそれから得られる軟磁性フィルムに関する。 The present invention relates to a soft magnetic thermosetting film and a soft magnetic film obtained therefrom.
　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（反対面）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 contains a soft magnetic material on the surface (opposite 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 a soft magnetic film 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
　ところで、軟磁性フィルムは、一般的に軟磁性粉末およびバインダ樹脂を含有する熱硬化性樹脂を加熱硬化することにより製造される。しかし、軟磁性フィルムは、加熱後、高温高湿雰囲気下に長期保存しておくと、比透磁率などの磁気特性が劣化する不具合が生じる。 By the way, a soft magnetic film is generally manufactured by heat-curing a thermosetting resin containing soft magnetic powder and a binder resin. However, if the soft magnetic film is stored for a long time in a high temperature and high humidity atmosphere after heating, there arises a problem that magnetic properties such as relative permeability deteriorate.
　本発明の目的は、高温高湿雰囲気下に長時間保存後においても、磁気特性の劣化が抑制される軟磁性熱硬化性フィルム及びそれから得られる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 thermosetting film in which deterioration of magnetic properties is suppressed even after being stored for a long time in a high temperature and high humidity atmosphere, and a soft magnetic film obtained therefrom.
　本発明の軟磁性熱硬化性フィルムは、軟磁性粒子を含有する軟磁性熱硬化性フィルムであって、前記軟磁性熱硬化性フィルムを加熱硬化した直後の周波数１ＭＨｚにおける初期比透磁率μ０´と、前記軟磁性熱硬化性フィルムを加熱硬化し、８５℃、８５％ＲＨの雰囲気下で１６８時間放置したときの周波数１ＭＨｚにおける比透磁率μ１´との比率（μ１´／μ０´）が０．８５以上であることを特徴としている。 The soft magnetic thermosetting film of the present invention is a soft magnetic thermosetting film containing soft magnetic particles, and has an initial relative magnetic permeability μ0 ′ at a frequency of 1 MHz immediately after the soft magnetic thermosetting film is heated and cured. The ratio (μ1 ′ / μ0 ′) of the relative magnetic permeability μ1 ′ at a frequency of 1 MHz when the soft magnetic thermosetting film was cured by heating and allowed to stand for 168 hours in an atmosphere of 85 ° C. and 85% RH was 0. It is characterized by being 85 or more.
　また、本発明の軟磁性熱硬化性フィルムは、前記軟磁性粒子を４０体積％以上含有する軟磁性熱硬化性組成物から形成されることが好適である。 The soft magnetic thermosetting film of the present invention is preferably formed from a soft magnetic thermosetting composition containing 40% by volume or more of the soft magnetic particles.
　また、本発明の軟磁性熱硬化性フィルムは、前記軟磁性熱硬化性組成物が、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することが好適である。 In the soft magnetic thermosetting film of the present invention, it is preferable that the soft magnetic thermosetting composition contains an epoxy resin, a phenol resin, and an acrylic resin.
　また、本発明の軟磁性フィルムは、上述の軟磁性熱硬化性フィルムを加熱硬化し、硬化状態にすることにより得られることを特徴としている。 Further, the soft magnetic film of the present invention is characterized by being obtained by heating and curing the above-mentioned soft magnetic thermosetting film.
　本発明の軟磁性熱硬化性フィルムを加熱硬化して得られる本発明の軟磁性フィルムは、高温高湿雰囲気下に長時間保存（放置）後においても、磁気特性の劣化が抑制され、良好な磁気特性を備える。 The soft magnetic film of the present invention obtained by heating and curing the soft magnetic thermosetting film of the present invention is excellent in that the deterioration of magnetic properties is suppressed even after storage (standing) for a long time in a high temperature and high humidity atmosphere. With magnetic properties.
　本発明の軟磁性熱硬化性フィルムは、例えば、軟磁性粒子および樹脂成分を含有する軟磁性熱硬化性組成物から形成される。 The soft magnetic thermosetting film of the present invention is formed from, for example, a soft magnetic thermosetting 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.
　これらの中でも、より好ましくは、Ｓｉ含有割合が９～１５質量％であるＦｅ－Ｓｉ－Ａｌ合金が挙げられる。これにより、軟磁性フィルムの磁性特性を向上することができる。 Among these, Fe—Si—Al alloys having a Si content of 9 to 15% by mass are more preferable. Thereby, the magnetic characteristics of the soft magnetic film can be improved.
　軟磁性粒子の形状としては、好ましくは、扁平状（板状）が挙げられる。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、軟磁性粒子の平均粒子径（平均長さ）の粒径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 shape of the soft magnetic particles is preferably a flat shape (plate shape). The flatness (flatness) is, for example, 8 or more, preferably 15 or more, and for example, 80 or less, preferably 65 or less. The aspect ratio is calculated as an aspect ratio obtained by dividing the particle diameter of 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. 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.
　軟磁性熱硬化性組成物（ひいては、軟磁性熱硬化性フィルムや軟磁性フィルム）における軟磁性粒子の質量割合は、例えば、７０質量％以上、好ましくは、８０質量％以上、より好ましくは、８５質量％以上であり、また、例えば、９５質量％以下、好ましくは、９２質量％以下、より好ましくは、９０質量％以下である。軟磁性熱硬化性組成物における軟磁性粒子の体積割合は、例えば、３０体積％以上、好ましくは、４０体積％以上、より好ましくは、５０体積％以上であり、また、例えば、８０体積％以下、好ましくは、７０体積％以下、より好ましくは、６０体積％以下である。上記上限以下の範囲とすることにより、軟磁性フィルムの成形性に優れる。一方、上記下限以上の範囲とすることにより、軟磁性フィルムの磁気特性に優れる。 The mass ratio of the soft magnetic particles in the soft magnetic thermosetting composition (and hence the soft magnetic thermosetting film or soft magnetic film) is, for example, 70% by mass or more, preferably 80% by mass or more, and more preferably 85%. For example, it is 95% by mass or less, preferably 92% by mass or less, and more preferably 90% by mass or less. The volume ratio of the soft magnetic particles in the soft magnetic thermosetting composition is, for example, 30% by volume or more, preferably 40% by volume or more, more preferably 50% by volume or more, and for example, 80% by volume or less. Preferably, it is 70 volume% or less, More preferably, it is 60 volume% or less. By making it into the range below the upper limit, the soft magnetic film is excellent in moldability. On the other hand, the soft magnetic film is excellent in the magnetic properties by setting the range to the above lower limit or more.
　樹脂成分は、熱硬化性樹脂を含有する。 The resin component contains a thermosetting resin.
　熱硬化性樹脂としては、エポキシ樹脂、フェノール樹脂、アミノ樹脂、不飽和ポリエステル樹脂、ポリウレタン樹脂、シリコーン樹脂、ユリア樹脂、メラミン樹脂、熱硬化性ポリイミド樹脂、ジアリルフタレート樹脂などが挙げられる。好ましくは、エポキシ樹脂、フェノール樹脂が挙げられ、より好ましくは、エポキシ樹脂およびフェノール樹脂の併用が挙げられる。これらは単独または２種以上を併用して用いることができる。 Examples of the thermosetting resin include epoxy resins, phenol resins, amino resins, unsaturated polyester resins, polyurethane resins, silicone resins, urea resins, melamine resins, thermosetting polyimide resins, diallyl phthalate resins, and the like. Preferably, an epoxy resin and a phenol resin are mentioned, More preferably, combined use of an epoxy resin and a phenol resin is mentioned. These can be used alone or in combination of two or more.
　エポキシ樹脂は、接着剤組成物として一般に用いられるものであれば限定されず、例えば、ビスフェノール型エポキシ樹脂（特に、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、ビスフェノールＳ型エポキシ樹脂、臭素化ビスフェノールＡ型エポキシ樹脂、水素添加ビスフェノールＡ型エポキシ樹脂、ビスフェノールＡＦ型エポキシ樹脂など）、フェノール型エポキシ樹脂（特に、フェノールノボラック型エポキシ樹脂、オルソクレゾールノボラック型エポキシ樹脂など）、ビフェニル型エポキシ樹脂、ナフタレン型エポキシ樹脂、フルオンレン型エポキシ樹脂、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の二官能エポキシ樹脂や多官能エポキシ樹脂が挙げられる。また、例えば、ヒダントイン型エポキシ樹脂、トリスグリシジルイソシアヌレート型エポキシ樹脂、グリシジルアミン型エポキシ樹脂なども挙げられる。これらは単独または２種以上を併用して用いることができる。 The epoxy resin is not limited as long as it is generally used as an adhesive composition. For example, bisphenol type epoxy resin (particularly, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, brominated bisphenol). A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol AF type epoxy resin, etc.), phenol type epoxy resin (especially phenol novolac type epoxy resin, orthocresol novolak type epoxy resin, etc.), biphenyl type epoxy resin, naphthalene type Bifunctional epoxy resins and polyfunctional epoxy resins such as epoxy resins, fluorene type epoxy resins, trishydroxyphenylmethane type epoxy resins, tetraphenylolethane type epoxy resins That. Moreover, for example, a hydantoin type epoxy resin, a trisglycidyl isocyanurate type epoxy resin, a glycidylamine type epoxy resin and the like can be mentioned. These can be used alone or in combination of two or more.
　これらのエポキシ樹脂のうち、好ましくは、ビスフェノール型エポキシ樹脂、ノボラック型エポキシ樹脂、オルソクレゾールノボラック型エポキシ樹脂、ビフェニル型エポキシ樹脂、トリスヒドロキシフェニルメタン型樹脂、テトラフェニロールエタン型エポキシ樹脂が挙げられ、より好ましくは、ビスフェノール型エポキシ樹脂が挙げられる。これらのエポキシ樹脂を含有させることより、フェノール樹脂との反応性が優れ、その結果、軟磁性熱硬化性フィルムを加熱硬化して得られる軟磁性フィルムにおいて、高温高湿雰囲気下での磁気特性の長期保存性に優れる。 Among these epoxy resins, preferably, bisphenol type epoxy resin, novolac type epoxy resin, orthocresol novolac type epoxy resin, biphenyl type epoxy resin, trishydroxyphenylmethane type resin, tetraphenylolethane type epoxy resin are mentioned, More preferably, a bisphenol type epoxy resin is mentioned. By including these epoxy resins, the reactivity with the phenol resin is excellent, and as a result, in the soft magnetic film obtained by heating and curing the soft magnetic thermosetting film, the magnetic properties in a high temperature and high humidity atmosphere are improved. Excellent long-term storage.
　フェノール樹脂は、エポキシ樹脂の硬化剤であり、例えば、フェノールノボラック樹脂、フェノールアラルキル樹脂、クレゾールノボラック樹脂、ｔｅｒｔ－ブチルフェノールノボラック樹脂、ノニルフェノールノボラック樹脂などのノボラック型フェノール樹脂、例えば、レゾール型フェノール樹脂、例えば、ポリパラオキシスチレンなどのポリオキシスチレンが挙げられる。これらは単独で使用また２種以上を併用することができる。これらのフェノール樹脂のうち、好ましくは、ノボラック型樹脂、より好ましくは、フェノールノボラック樹脂、フェノールアラルキル樹脂、さらに好ましくは、フェノールアラルキル樹脂が挙げられる。これらのフェノール樹脂を含有することより、エポキシ樹脂との反応性が優れ、その結果、軟磁性フィルムが長期保存性に優れる。　 The phenol resin is a curing agent for an epoxy resin. For example, a phenol novolak resin, a phenol aralkyl resin, a cresol novolak resin, a tert-butylphenol novolak resin, a novolak type phenol resin such as a nonylphenol novolak resin, for example, a resol type phenol resin, for example, And polyoxystyrene such as polyparaoxystyrene. These can be used alone or in combination of two or more. Among these phenol resins, a novolak resin is preferable, a phenol novolac resin, a phenol aralkyl resin, and more preferably a phenol aralkyl resin. By containing these phenol resins, the reactivity with the epoxy resin is excellent, and as a result, the soft magnetic film is excellent in long-term storage stability. *
　樹脂成分が、エポキシ樹脂およびフェノール樹脂を併用するとき、エポキシ樹脂のエポキシ当量１００ｇ／ｅｑに対するフェノール樹脂の水酸基当量が１ｇ／ｅｑ以上１００ｇ／ｅｑ未満である場合、樹脂成分１００質量部に対するエポキシ樹脂の含有割合は、例えば、１５質量部以上、好ましくは、３０質量部以上であり、また、例えば、７０質量部以下、好ましくは、５０質量部以下、より好ましくは、４０質量部以下でもあり、樹脂成分１００質量部に対するフェノール樹脂の含有割合は、例えば、５質量部以上、好ましくは、１５質量部以上であり、また、例えば、３０質量部以下、好ましくは、２０質量部以下である。 When the resin component is used in combination with an epoxy resin and a phenol resin, when the hydroxyl equivalent of the phenol resin to the epoxy equivalent of 100 g / eq of the epoxy resin is 1 g / eq or more and less than 100 g / eq, The content ratio is, for example, 15 parts by mass or more, preferably 30 parts by mass or more, and for example, 70 parts by mass or less, preferably 50 parts by mass or less, more preferably 40 parts by mass or less. The content rate of the phenol resin with respect to 100 mass parts of components is 5 mass parts or more, for example, Preferably, it is 15 mass parts or more, for example, is 30 mass parts or less, Preferably, it is 20 mass parts or less.
　エポキシ樹脂のエポキシ当量１００ｇ／ｅｑに対するフェノール樹脂の水酸基当量が１００ｇ／ｅｑ以上２００ｇ／ｅｑ未満である場合、樹脂成分１００質量部に対するエポキシ樹脂の含有割合は、例えば、１０質量部以上、好ましくは、２５質量部以上であり、また、例えば、５０質量部以下でもあり、樹脂成分１００質量部に対するフェノール樹脂の含有割合は、例えば、１０質量部以上、好ましくは、２５質量部以上であり、また、例えば、５０質量部以下である。 When the hydroxyl group equivalent of the phenol resin with respect to the epoxy equivalent of 100 g / eq of the epoxy resin is 100 g / eq or more and less than 200 g / eq, the content of the epoxy resin with respect to 100 parts by mass of the resin component is, for example, 10 parts by mass or more, 25 parts by mass or more, for example, 50 parts by mass or less, and the content ratio of the phenol resin to 100 parts by mass of the resin component is, for example, 10 parts by mass or more, preferably 25 parts by mass or more. For example, it is 50 parts by mass or less.
　エポキシ樹脂のエポキシ当量１００ｇ／ｅｑに対するフェノール樹脂の水酸基当量が２００ｇ／ｅｑ以上１０００ｇ／ｅｑ以下である場合、樹脂成分１００質量部に対するエポキシ樹脂の含有割合は、例えば、５質量部以上、好ましくは、１５質量部以上であり、また、例えば、３０質量部以下でもあり、樹脂成分１００質量部に対するフェノール樹脂の含有割合は、例えば、１５質量部以上、好ましくは、３５質量部以上であり、また、例えば、７０質量部以下である。 When the hydroxyl group equivalent of the phenol resin with respect to the epoxy equivalent of 100 g / eq of the epoxy resin is 200 g / eq or more and 1000 g / eq or less, the content of the epoxy resin with respect to 100 parts by mass of the resin component is, for example, 5 parts by mass or more, 15 parts by mass or more, for example, 30 parts by mass or less, and the content ratio of the phenol resin to 100 parts by mass of the resin component is, for example, 15 parts by mass or more, preferably 35 parts by mass or more. For example, it is 70 parts by mass or less.
　なお、エポキシ樹脂が２種併用される場合のエポキシ当量は、各エポキシ樹脂のエポキシ当量に、エポキシ樹脂の総量に対する各エポキシ樹脂の質量割合を乗じて、それらを合算した全エポキシ樹脂のエポキシ当量である。 In addition, the epoxy equivalent when two types of epoxy resins are used in combination is the epoxy equivalent of all epoxy resins obtained by multiplying the epoxy equivalent of each epoxy resin by the mass ratio of each epoxy resin to the total amount of epoxy resin, and adding them together. is there.
　また、フェノール樹脂中の水酸基当量は、エポキシ樹脂のエポキシ基１当量当たり、例えば、０．２当量以上、好ましくは、０．５当量以上であり、また、例えば、２．０当量以下、好ましくは、１．２当量以下である。水酸基の量が上記範囲内であると、軟磁性熱硬化性フィルムの硬化反応が良好となり、また、劣化を抑制することができる。 Further, the hydroxyl group equivalent in the phenol resin is, for example, 0.2 equivalents or more, preferably 0.5 equivalents or more, and preferably, 2.0 equivalents or less, preferably 1 equivalent or less, per equivalent of epoxy group of the epoxy resin. 1.2 equivalents or less. When the amount of the hydroxyl group is within the above range, the curing reaction of the soft magnetic thermosetting film becomes good, and deterioration can be suppressed.
　樹脂成分は、熱硬化性樹脂に加えて、好ましくは、アクリル樹脂を含有する。より好ましくは、アクリル樹脂、エポキシ樹脂およびフェノール樹脂を併用する。さらに好ましくは、樹脂成分は、エポキシ樹脂、フェノール樹脂およびアクリル樹脂のみからなる。樹脂成分が、これらの樹脂を含有することにより、軟磁性熱硬化性フィルムを複数積層させ、熱プレスすることにより、一枚の軟磁性フィルムを製造する際に、積層界面にむらがなく均一で、磁気特性が良好な軟磁性フィルムを得ることができる。 The resin component preferably contains an acrylic resin in addition to the thermosetting resin. More preferably, an acrylic resin, an epoxy resin, and a phenol resin are used in combination. More preferably, the resin component consists only of an epoxy resin, a phenol resin, and an acrylic resin. When the resin component contains these resins, a plurality of soft magnetic thermosetting films are laminated and hot pressed to produce a single soft magnetic film, which is uniform and uniform at the lamination interface. A soft magnetic film with good magnetic properties can be obtained.
　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, octyl, isooctyl, nonyl, isononyl, decyl, isodecyl, undecyl, lauryl, tridecyl, tetradecyl, stearyl, octadecyl, dodecyl 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、アクリロニトリルなどが挙げられる。 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 monomers such as (meth) acryloyloxynaphthalene sulfonic acid, and phosphoric acid group-containing monomers such as 2-hydroxyethylacryloyl phosphate, such as styrene monomer and acrylonitrile.
　これらの中でも、好ましくは、グリシジル基含有モノマー、カルボキシル基含有モノマーまたはヒドロキシル基含有モノマーが挙げられる。アクリル樹脂が（メタ）アクリル酸アルキルエステルとこれらのその他のモノマーとの共重合体である場合、すなわち、アクリル樹脂がグリシジル基、カルボキシル基またはヒドロキシル基を有する場合、軟磁性フィルムの耐リフロー性がより一層優れる。 Among these, Preferably, a glycidyl group-containing monomer, a carboxyl group-containing monomer, or a hydroxyl group-containing monomer is used. When the acrylic resin is a copolymer of (meth) acrylic acid alkyl ester and these other monomers, that is, when the acrylic resin has a glycidyl group, a carboxyl group or a hydroxyl group, the reflow resistance of the soft magnetic film is Even better.
　（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る場合、その他のモノマーの配合割合（質量）は、共重合体に対して、好ましくは、４０質量％以下である。 In the case of a copolymer of (meth) acrylic acid alkyl ester and other monomer, the blending ratio (mass) of the other monomer is preferably 40% by mass or less with respect to the copolymer.
　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。この範囲とすることにより、軟磁性熱硬化性フィルムの接着性および耐リフロー性に優れる。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. By setting it as this range, it is excellent in the adhesiveness and reflow resistance of a soft-magnetic thermosetting film. 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点（Ｔｇ）は、例えば、－３０℃以上、好ましくは、－２０℃以上であり、また、例えば、３０℃以下、好ましくは、１５℃以下である。上記下限以上であると、軟磁性熱硬化性フィルムの接着性に優れる。一方、上記上限以下であると、軟磁性熱硬化性フィルムの取扱い性に優れる。なお、ガラス転移点は、動的粘弾性測定装置（ＤＭＡ、周波数１Ｈｚ、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 point (Tg) of the acrylic resin is, for example, −30 ° C. or more, preferably −20 ° C. or more, and for example, 30 ° C. or less, preferably 15 ° C. or less. It is excellent in the adhesiveness of a soft-magnetic thermosetting film as it is more than the said minimum. On the other hand, it is excellent in the handleability of a soft-magnetic thermosetting film as it is below the said upper limit. The glass transition point is obtained from the maximum value of the loss tangent (tan δ) measured using a dynamic viscoelasticity measuring device (DMA, frequency 1 Hz, heating rate 10 ° C./min).
　樹脂成分がアクリル樹脂を含有する場合、樹脂成分における熱硬化性樹脂の含有割合は、例えば、３５質量％以上、好ましくは、５０質量％を超過し、より好ましくは、５２質量％以上である。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、６０質量％以下である。熱硬化性樹脂の含有割合が上記範囲である場合、特に熱硬化性樹脂リッチ（５０質量％超）である場合、吸水や熱による樹脂の膨張、ひいては、軟磁性フィルムの空隙の発生を効果的に抑制することができるため、高温高湿雰囲気下での磁気特性の長期保存性が優れる。 When the resin component contains an acrylic resin, the content ratio of the thermosetting resin in the resin component is, for example, 35% by mass or more, preferably more than 50% by mass, and more preferably 52% by mass or more. For example, it is 90 mass% or less, Preferably, it is 80 mass% or less, More preferably, it is 60 mass% or less. When the content ratio of the thermosetting resin is within the above range, particularly when the thermosetting resin is rich (over 50% by mass), it is effective for the expansion of the resin due to water absorption or heat, and hence the generation of voids in the soft magnetic film. Therefore, long-term storage stability of magnetic properties in a high-temperature and high-humidity atmosphere is excellent.
　樹脂成分におけるアクリル樹脂の含有割合は、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、４０質量％以上であり、また、例えば、６５質量％以下、好ましくは、５０質量％未満、より好ましくは、４８質量％以下である。 The content ratio of the acrylic resin in the resin component is, for example, 10% by mass or more, preferably 20% by mass or more, more preferably 40% by mass or more, and for example, 65% by mass or less, preferably 50% by mass. %, More preferably 48% by mass or less.
　軟磁性熱硬化性組成物における樹脂成分の含有割合は、例えば、５質量％以上、好ましくは、８質量％以上、より好ましくは、１０質量％以上であり、また、例えば、３０質量％以下、好ましくは、２０質量％以下、より好ましくは、１５質量％以下である。上記範囲とすることにより、軟磁性フィルムの成膜性、磁気特性に優れる。 The content ratio of the resin component in the soft magnetic thermosetting composition is, for example, 5% by mass or more, preferably 8% by mass or more, more preferably 10% by mass or more, and for example, 30% by mass or less. Preferably, it is 20 mass% or less, More preferably, it is 15 mass% or less. By setting it within the above range, the soft magnetic film is excellent in film formability and magnetic properties.
　また、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）の含有割合は、軟磁性熱硬化性組成物から軟磁性粒子を除いた軟磁性粒子除外成分１００質量部に対して、例えば、２０質量部以上、好ましくは、３０質量部以上、より好ましくは、４０質量部以上、さらに好ましくは、５０質量部を超過し、最も好ましくは、５２質量部以上であり、また、例えば、９９質量部以下、好ましくは、９０質量部以下、より好ましくは、８０質量部以下、さらに好ましくは、７０質量部以下、最も好ましくは、６０質量部以下である。上記範囲とすることにより、軟磁性フィルムが、高温高湿雰囲気下での磁気特性の長期保存性に優れる。 The content of the thermosetting resin (preferably, a thermosetting resin made of an epoxy resin and a phenol resin) is 100 mass parts of the soft magnetic particle excluded component obtained by removing the soft magnetic particles from the soft magnetic thermosetting composition. On the other hand, for example, 20 parts by mass or more, preferably 30 parts by mass or more, more preferably 40 parts by mass or more, still more preferably more than 50 parts by mass, most preferably 52 parts by mass or more, For example, it is 99 parts by mass or less, preferably 90 parts by mass or less, more preferably 80 parts by mass or less, still more preferably 70 parts by mass or less, and most preferably 60 parts by mass or less. By setting it as the said range, a soft-magnetic film is excellent in the long-term storage property of the magnetic characteristic in a high-temperature, high-humidity atmosphere.
　なお、軟磁性粒子除外成分は、より具体的には、樹脂成分、必要に応じて添加される熱硬化触媒（後述）および添加剤（後述）からなる成分であって、軟磁性粒子および溶媒は含まれない。　 More specifically, the soft magnetic particle exclusion component is a component composed of a resin component, a thermosetting catalyst (described later) and an additive (described later) that are added as necessary, and the soft magnetic particles and the solvent include Not included. *
　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熱可塑性樹脂を含有することもできる。 The resin component can also contain other thermoplastic resins other than thermosetting resins and acrylic resins.
　このような熱可塑性樹脂としては、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、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。これらの樹脂は、単独で使用又は２種以上を併用することができる。 Examples of such thermoplastic resins include natural rubber, butyl rubber, isoprene rubber, chloroprene rubber, ethylene-vinyl acetate copolymer, copolymer, polybutadiene resin, polycarbonate resin, thermoplastic polyimide resin, polyamide resin (6- Nylon, 6,6-nylon, etc.), phenoxy resin, saturated polyester resin (PET, PBT, etc.), polyamideimide resin, fluororesin and the like. These resins can be used alone or in combination of two or more.
　軟磁性熱硬化性組成物は、好ましくは、熱硬化性触媒を含有する。 The soft magnetic thermosetting 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、イミダゾール骨格を有する塩、トリフェニルフォスフィン構造を有する塩、トリフェニルボラン構造を有する塩、アミノ基含有化合物などが挙げられる。好ましくは、イミダゾール骨格を有する塩が挙げられる。 The thermosetting catalyst is not limited as long as it is a catalyst that accelerates the curing of the resin component by heating. For example, a salt having an imidazole skeleton, a salt having a triphenylphosphine structure, a salt having a triphenylborane structure, amino And group-containing compounds. Preferably, a salt having an imidazole skeleton is used.
　イミダゾール骨格を有する塩としては、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－４，５－ジヒドロキシメチルイミダゾール（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）。熱硬化触媒は、単独で使用または２種類以上併用することができる。 Examples of the salt having an imidazole skeleton include 2-phenylimidazole (trade name; 2PZ), 2-ethyl-4-methylimidazole (trade name; 2E4MZ), 2-methylimidazole (trade name; 2MZ), 2-un Decylimidazole (trade name; C11Z), 2-phenyl-4,5-dihydroxymethylimidazole (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.). A thermosetting catalyst can be used individually or can be used together 2 or more types.
　熱硬化触媒の形状は、例えば、球状、楕円体状などが挙げられる。 Examples of the shape of the thermosetting catalyst include a spherical shape and an ellipsoidal shape.
　熱硬化触媒の配合割合は、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。熱硬化触媒の配合割合が上記範囲内とすることにより、軟磁性熱硬化性フィルムを低温度かつ短時間で加熱硬化することができ、また、高温高湿雰囲気下での磁気特性の長期保存性および耐リフロー性に優れる。 The blending ratio of the thermosetting catalyst is, for example, 0.1 parts by mass or more, preferably 0.3 parts by mass or more, for example, 5 parts by mass or less, preferably 100 parts by mass of the resin component. 3 parts by mass or less. When the blending ratio of the thermosetting catalyst is within the above range, the soft magnetic thermosetting film can be cured by heating at a low temperature and in a short time, and the magnetic properties can be stored for a long time in a high temperature and high humidity atmosphere. Excellent reflow resistance.
　軟磁性熱硬化性組成物は（ひいては、軟磁性熱硬化性フィルムおよび軟磁性フィルム）、必要に応じて、分散剤、架橋剤、無機充填材などの市販または公知の添加剤を含有することもできる。 The soft magnetic thermosetting composition (and thus the soft magnetic thermosetting film and the soft magnetic film) may contain a commercially available or known additive such as a dispersant, a crosslinking agent, and an inorganic filler, if necessary. it can.
　軟磁性熱硬化性組成物は、好ましくは、分散剤を含有する。 The soft magnetic thermosetting composition preferably contains a dispersant.
　分散剤としては、例えば、ポリエーテルリン酸エステル、シランカップリング剤、チタネートカップリング剤が挙げられる。好ましくは、ポリエーテルリン酸エステルが挙げられる。軟磁性熱硬化性組成物が分散剤、特にポリエーテルリン酸エステルを含有することにより、軟磁性熱硬化性組成物の塗工性を向上させるとともに、軟磁性フィルムの磁気特性をより一層向上させることができる。 Examples of the dispersant include polyether phosphate esters, silane coupling agents, and titanate coupling agents. Preferably, polyether phosphate ester is mentioned. When the soft magnetic thermosetting composition contains a dispersant, particularly a polyether phosphate, the coating property of the soft magnetic thermosetting composition is improved and the magnetic properties of the soft magnetic film are further improved. be able to.
　ポリエーテルリン酸エステルとしては、例えば、ポリオキシアルキレンアルキルエーテルリン酸エステル、ポリオキシアルキレンアルキルフェニルエーテルリン酸エステルなどが挙げられる。好ましくは、ポリオキシアルキレンアルキルエーテルリン酸エステルが挙げられる。 Examples of polyether phosphate esters include polyoxyalkylene alkyl ether phosphate esters and polyoxyalkylene alkyl phenyl ether phosphate esters. Preferably, polyoxyalkylene alkyl ether phosphate ester is used.
　ポリオキシアルキレンアルキルエーテルリン酸エステルは、アルキル－オキシ－ポリ（アルキレンオキシ）基が、リン酸塩のリン原子に、１～３個結合している形態を有している。このようなアルキル－オキシ－ポリ（アルキレンオキシ）基［すなわち、ポリオキシアルキレンアルキルエーテル部位］において、ポリ（アルキレンオキシ）部位に関するアルキレンオキシの繰り返し数としては、特に制限されないが、例えば、２～３０（好ましくは３～２０）の範囲から適宜選択することができる。ポリ（アルキレンオキシ）部位のアルキレンとしては、好ましくは、炭素数が、２～４のアルキレン基が挙げられる。具体的には、エチレン基、プロピレン基、イソプロピレン基、ブチレン基、イソブチル基などが挙げられる。また、アルキル基としては、特に制限されないが、例えば、好ましくは、炭素数が６～３０のアルキル基、より好ましくは、８～２０のアルキル基が挙げられる。具体的には、アルキル基としては、例えば、デシル基、ウンデシル基、ドデシル基、トリデシル基、テトラデシル基、ペンタデシル基、ヘキサデシル基、ヘプタデシル基、オクタデシル基などが挙げられる。なお、ポリオキシアルキレンアルキルエーテルリン酸エステルが複数のアルキル－オキシ－ポリ（アルキレンオキシ）基を有している場合、複数のアルキル基は、異なっていてもよいが、同一であってもよい。なお、ポリエーテルリン酸エステルは、アミンなどとの混合物であってもよい。 The polyoxyalkylene alkyl ether phosphate ester has a form in which 1 to 3 alkyl-oxy-poly (alkyleneoxy) groups are bonded to the phosphorus atom of the phosphate. In such an alkyl-oxy-poly (alkyleneoxy) group [ie, a polyoxyalkylene alkyl ether moiety], the number of repeating alkyleneoxy with respect to the poly (alkyleneoxy) moiety is not particularly limited. It can be appropriately selected from the range of (preferably 3 to 20). The alkylene at the poly (alkyleneoxy) moiety is preferably an alkylene group having 2 to 4 carbon atoms. Specific examples include an ethylene group, a propylene group, an isopropylene group, a butylene group, and an isobutyl group. Further, the alkyl group is not particularly limited, and for example, an alkyl group having 6 to 30 carbon atoms is preferable, and an alkyl group having 8 to 20 carbon atoms is more preferable. Specifically, examples of the alkyl group include a decyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, and an octadecyl group. When the polyoxyalkylene alkyl ether phosphate ester has a plurality of alkyl-oxy-poly (alkyleneoxy) groups, the plurality of alkyl groups may be different or the same. The polyether phosphate ester may be a mixture with an amine or the like.
　ポリエーテルリン酸エステルの酸価は、例えば、１０以上、好ましくは、１５以上であり、また、例えば、２００以下、好ましくは、１５０以下である。酸価は、中和滴定法などによって測定される。 The acid value of the polyether phosphate ester is, for example, 10 or more, preferably 15 or more, and for example, 200 or less, preferably 150 or less. The acid value is measured by a neutralization titration method or the like.
　シランカップリング剤としては、例えば、３－メタクリロキシプロピルトリメトキシシラン、２－（３，４－エポキシシクロヘキシル）エチルトリメトキシシランなどが挙げられる。 Examples of the silane coupling agent include 3-methacryloxypropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and the like.
　分散剤は、単独で使用または２種類以上併用することができる。 Dispersants can be used alone or in combination of two or more.
　分散剤の具体例として、楠本化成社のＨＩＰＬＡＡＤシリーズ（「ＥＤ１５２」、「ＥＤ１５３」、「ＥＤ１５４」、「ＥＤ１１８」、「ＥＤ１７４」、「ＥＤ２５１」）、信越化学社製のＫＢＭシリーズ（「ＫＢＭ３０３」、「ＫＢＭ５０３」）などが挙げられる。 Specific examples of the dispersant include HIPLAAD series ("ED152", "ED153", "ED154", "ED118", "ED174", "ED251") from Enomoto Kasei Co., Ltd., KBM series ("KBM303") from Shin-Etsu Chemical Co., Ltd. , “KBM503”).
　分散剤の含有割合は、軟磁性粒子１００質量部に対し、例えば、０．１質量部以上、好ましくは、０．２質量部以上である。また、例えば、５質量部以下、好ましくは、２質量部以下である。 The content ratio of the dispersant is, for example, 0.1 parts by mass or more, preferably 0.2 parts by mass or more with respect to 100 parts by mass of the soft magnetic particles. For example, it is 5 mass parts or less, Preferably, it is 2 mass parts or less.
　軟磁性熱硬化性組成物は、上記成分を上記含有割合で混合することにより調製することができる。 The soft magnetic thermosetting composition can be prepared by mixing the above components in the above content ratio.
　次に、本発明の軟磁性熱硬化性フィルムの製造方法について説明する。 Next, a method for producing the soft magnetic thermosetting film of the present invention will be described.
　軟磁性熱硬化性フィルムを作製するには、上記した軟磁性熱硬化性組成物を溶媒に溶解または分散させた軟磁性熱硬化性組成物溶液を調製する。 In order to produce a soft magnetic thermosetting film, a soft magnetic thermosetting composition solution in which the above-described soft magnetic thermosetting composition is dissolved or dispersed in a solvent 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.
　軟磁性熱硬化性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 thermosetting 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、軟磁性熱硬化性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。これにより、軟磁性熱硬化性フィルムが得られる。 Next, the soft magnetic thermosetting composition solution is applied to the surface of a release substrate (separator, core material, etc.) and dried. Thereby, a soft magnetic thermosetting film is obtained.
　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分間以下である。 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 thereof include a resin substrate reinforced with a woven fiber, a silicon substrate, a glass substrate, 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、軟磁性熱硬化性フィルムを得る。 Thereby, a soft magnetic thermosetting film is obtained.
　軟磁性熱硬化性フィルムは、室温（具体的には、２５℃）において、半硬化状態（Ｂステージ状態）であり、良好な接着性を備える軟磁性熱硬化性接着フィルムである。 The soft magnetic thermosetting film is a soft magnetic thermosetting adhesive film that is in a semi-cured state (B stage state) at room temperature (specifically, 25 ° C.) and has good adhesiveness.
　また、軟磁性熱硬化性フィルムは、好ましくは、扁平状軟磁性粒子が含有され、その扁平状軟磁性粒子が、軟磁性熱硬化性フィルムの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）が軟磁性熱硬化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、軟磁性熱硬化性フィルムは、軟磁性粒子が高割合で充填され、磁気特性に優れる。また、薄膜化が図られている。 The soft magnetic thermosetting film preferably contains flat soft magnetic particles, and the flat soft magnetic particles are arranged in the two-dimensional in-plane direction of the soft magnetic thermosetting 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 thermosetting film. As a result, the soft magnetic thermosetting film is filled with soft magnetic particles at a high ratio and has excellent magnetic properties. Moreover, thinning is achieved.
　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.
　本発明の軟磁性熱硬化性フィルムは、例えば、軟磁性熱硬化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熱硬化性フィルムが積層された多層構造、軟磁性熱硬化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。 The soft magnetic thermosetting film of the present invention has, for example, a single-layer structure composed of only a single layer of a soft magnetic thermosetting film, a multilayer structure in which a soft magnetic thermosetting film is laminated on one or both sides of a core material, A multi-layer structure in which separators are laminated on one side or both sides of a magnetic thermosetting film can be used.
　次いで、本発明の軟磁性フィルムについて説明する。 Next, the soft magnetic film of the present invention will be described.
　軟磁性フィルムは、上記の軟磁性熱硬化性フィルムから形成される。具体的には、軟磁性フィルムは、上記の軟磁性熱硬化性フィルムを加熱硬化することにより得られる。 The soft magnetic film is formed from the above soft magnetic thermosetting film. Specifically, the soft magnetic film can be obtained by heat curing the soft magnetic thermosetting film.
　好ましくは、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、軟磁性熱硬化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。 Preferably, a plurality of 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 soft magnetic thermosetting film can be filled with soft magnetic particles at a high rate, and the magnetic properties can be improved.
　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、半硬化状態の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 in a semi-cured state is cured by heating, and a soft magnetic film in a cured state (C stage state) is obtained.
　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.
　軟磁性フィルムにおける、加熱硬化された直後（具体的には、軟磁性熱硬化性フィルムを加熱硬化した後３０分以内）の周波数１ＭＨｚにおける比透磁率（初期比透磁率μ０´）は、例えば、１００以上、好ましくは、１５０以上、より好ましくは、１８０以上であり、また、例えば、４００以下である。 In the soft magnetic film, the relative permeability (initial relative permeability μ0 ′) at a frequency of 1 MHz immediately after being heat-cured (specifically, within 30 minutes after heat-curing the soft magnetic thermosetting film) is, for example, 100 or more, preferably 150 or more, more preferably 180 or more, and for example, 400 or less.
　加熱硬化後、８５℃、８５％ＲＨの雰囲気下で１６８時間放置したときの周波数１ＭＨｚにおける比透磁率（比透磁率μ１´）は、例えば、１００以上、好ましくは、１５０以上、より好ましくは、１８０以上であり、また、例えば、４００以下である。 After heat curing, the relative permeability (relative permeability μ1 ′) at a frequency of 1 MHz when left in an atmosphere of 85 ° C. and 85% RH for 168 hours is, for example, 100 or more, preferably 150 or more, more preferably 180 or more, for example, 400 or less.
　また、初期比透磁率μ０´と比透磁率μ１´との比率（μ１´／μ０´）は、０．８５以上、好ましくは、０．９０以上、より好ましくは、０．９５以上、さらに好ましくは、０．９６以上、最も好ましくは、０．９７以上であり、また、例えば、１．００以下である。上記比率を上記範囲内とすることにより、軟磁性フィルムが、高温高湿雰囲気下での磁気特性の長期保存性に優れる。 In addition, the ratio (μ1 ′ / μ0 ′) between the initial relative permeability μ0 ′ and the relative permeability μ1 ′ is 0.85 or more, preferably 0.90 or more, more preferably 0.95 or more, and still more preferably Is 0.96 or more, most preferably 0.97 or more, and for example, 1.00 or less. By setting the ratio within the above range, the soft magnetic film is excellent in long-term storage stability of magnetic properties in a high temperature and high humidity atmosphere.
　比透磁率（μ０´およびμ１´）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 (μ0 ′ and μ1 ′) is measured by an one-turn method (frequency 1 MHz) using an impedance analyzer (manufactured by Agilent, “4294A”).
　また、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。このため、軟磁性フィルムは、薄膜であり、比透磁率が優れる。 In the soft magnetic film, preferably, the soft magnetic particles contained in the soft magnetic film are 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. For this reason, the soft magnetic film is a thin film and has excellent relative magnetic permeability.
　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. .
　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（磁性フィルム）として好適に用いることができる。より具体的には、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。 This soft magnetic film can be suitably used as, for example, an antenna, a coil, or a soft magnetic film (magnetic film) to be laminated on a circuit board on which these are formed. More specifically, it can be used for applications such as smartphones, personal computers, and position detection devices.
　軟磁性フィルムを回路基板に積層させるためには、軟磁性フィルムを接着剤層を介して回路基板に固定する方法、軟磁性熱硬化性フィルムを回路基板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させて軟磁性フィルムにするとともに回路基板に固定する方法などが挙げられる。 In order to laminate a soft magnetic film on a circuit board, a method of fixing the soft magnetic film to the circuit board through an adhesive layer, a soft magnetic thermosetting film directly attached to the circuit board, Examples thereof include a method in which a curable film is cured by heating to form a soft magnetic film and fixed to a circuit board.
　接着剤層が不要であり電子機器を小型化できる観点からは、好ましくは、軟磁性熱硬化性フィルムを回路基板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させる方法が挙げられる。 From the viewpoint of eliminating the need for an adhesive layer and reducing the size of an electronic device, a method in which a soft magnetic thermosetting film is directly attached to a circuit board and then the soft magnetic thermosetting film is cured by heating is preferable. It is done.
　また、絶縁性の観点からは、好ましくは、軟磁性フィルムを接着剤層を介して回路基板に固定する方法が挙げられる。 Also, from the viewpoint of insulation, a method of fixing the soft magnetic film to the circuit board through an adhesive layer is preferable.
　接着剤層は、回路基板の接着剤層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。接着剤層の厚みは、例えば、１０～１００μｍである。 As the adhesive layer, a known one that is usually used as an adhesive layer of a circuit board is used. For example, by applying and drying an adhesive such as an epoxy adhesive, a polyimide adhesive, or an acrylic adhesive It is formed. The thickness of the adhesive layer is, for example, 10 to 100 μm.
　そして、この軟磁性熱硬化性フィルムによれば、初期比透磁率μ０´と比透磁率μ１´との比率（μ１´／μ０´）が０．８５以上であるため、軟磁性熱硬化性フィルムを加熱硬化して得られる軟磁性フィルムを高温高湿雰囲気下に長時間保存した場合であっても、その軟磁性フィルムの比透磁率の劣化を抑制することができる。これにより、長期間優れた磁気特性を発揮することができる。 And according to this soft magnetic thermosetting film, since the ratio (μ1 ′ / μ0 ′) between the initial relative permeability μ0 ′ and the relative permeability μ1 ′ is 0.85 or more, the soft magnetic thermosetting film Even when a soft magnetic film obtained by heat curing is stored in a high temperature and high humidity atmosphere for a long time, deterioration of the relative magnetic permeability of the soft magnetic film can be suppressed. Thereby, excellent magnetic properties can be exhibited for a long time.
　高温高湿雰囲気下における耐性温度は、例えば、５０℃以上、好ましくは、８０℃以上であり、また、例えば、１５０℃以下、好ましくは、１００℃以下である。 Resistance temperature in a high temperature and high humidity atmosphere is, for example, 50 ° C. or higher, preferably 80 ° C. or higher, and for example, 150 ° C. or lower, preferably 100 ° C. or lower.
　高温高湿雰囲気下における耐性湿度は、例えば、５０％ＲＨ以上、好ましくは、８０％ＲＨ以上であり、また、例えば、１００％ＲＨ以下、好ましくは、９０％ＲＨ以下である。 Resistance humidity in a high temperature and high humidity atmosphere is, for example, 50% RH or more, preferably 80% RH or more, and, for example, 100% RH or less, preferably 90% RH or less.
　高温高湿雰囲気下における保存可能時間は、例えば、９６時間以上、好ましくは、１６８時間以上、より好ましくは、４００時間以上、さらに好ましくは、７００時間以上である。 The storable time in a high temperature and high humidity atmosphere is, for example, 96 hours or more, preferably 168 hours or more, more preferably 400 hours or more, and further preferably 700 hours or more.
　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。以下に示す実施例の数値は、上記の実施形態において記載される数値（すなわち、上限値または下限値）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. The numerical values in the following examples can be substituted for the numerical values (that is, the upper limit value or the lower limit value) described in the above embodiment.
　　実施例１
　（軟磁性熱硬化性フィルム）
　軟磁性熱硬化性組成物に対し軟磁性粒子が４０体積％となるように、軟磁性粒子５００質量部、アクリル酸エステル系ポリマー２２質量部、ビスフェノールＡ型エポキシ樹脂（「エピコート１００４」）４５質量部、ビスフェノールＡ型エポキシ樹脂（「エピコートＹＬ９８０」）２６質量部、フェノールアラルキル樹脂３２質量部、２－フェニル－４，５－ジヒドロキシメチルイミダゾール（「２ＰＨＺ－ＰＷ」熱硬化触媒）１．２６質量部（樹脂成分１００質量部に対して１．０質量部）、および、ポリエーテルリン酸エステル（分散剤）２．５質量部（軟磁性粒子１００質量部に対して０．５質量部）を混合することにより、軟磁性熱硬化性組成物を得た。 Example 1
(Soft magnetic thermosetting film)
Soft magnetic particles 500 parts by mass, acrylic ester polymer 22 parts by mass, bisphenol A type epoxy resin (“Epicoat 1004”) 45 parts by mass so that the soft magnetic particles are 40% by volume with respect to the soft magnetic thermosetting composition. Parts, 26 parts by mass of bisphenol A type epoxy resin (“Epicoat YL980”), 32 parts by mass of phenol aralkyl resin, 1.26 parts by mass of 2-phenyl-4,5-dihydroxymethylimidazole (“2PHZ-PW” thermosetting catalyst) (1.0 part by mass with respect to 100 parts by mass of resin component) and 2.5 parts by mass of polyether phosphate ester (dispersant) (0.5 parts by mass with respect to 100 parts by mass of soft magnetic particles) As a result, a soft magnetic thermosetting composition was obtained.
　この軟磁性熱硬化性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４３質量％の軟磁性熱硬化性組成物溶液を調製した。 This soft magnetic thermosetting composition was dissolved in methyl ethyl ketone to prepare a soft magnetic thermosetting composition solution having a solid content of 43% by mass.
　この軟磁性熱硬化性組成物溶液を、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からなるセパレータ（平均厚みが５０μｍ）上に塗布し、その後、１３０℃で２分間乾燥させた。 This soft magnetic thermosetting composition solution was applied onto a separator (average thickness: 50 μm) made of a polyethylene terephthalate film subjected to silicone release treatment, and then dried at 130 ° C. for 2 minutes.
　これにより、セパレータが積層された軟磁性熱硬化性フィルム（軟磁性熱硬化性フィルムのみの平均厚み、９０μｍ）を製造した。 Thereby, a soft magnetic thermosetting film (average thickness of only the soft magnetic thermosetting film, 90 μm) on which the separator was laminated was manufactured.
　（軟磁性フィルム）
　次いで、この軟磁性熱硬化性フィルムを、４層積層し、１７５℃、３０分、２０ＭＰａの条件で熱プレスにより加熱硬化させることにより、軟磁性フィルムを作製した。 (Soft magnetic film)
Next, four layers of this soft magnetic thermosetting film were laminated and heated and cured by hot pressing under the conditions of 175 ° C., 30 minutes, and 20 MPa to produce a soft magnetic film.
　　実施例２～４
　表１に記載の材料および配合割合で、軟磁性熱硬化性組成物を得た。この軟磁性熱硬化性組成物を用いた以外は、実施例１と同様にして、実施例２～４の軟磁性熱硬化性フィルムおよび熱硬化性フィルムを製造した。 Examples 2-4
Soft magnetic thermosetting compositions were obtained with the materials and blending ratios shown in Table 1. Soft magnetic thermosetting films and thermosetting films of Examples 2 to 4 were produced in the same manner as in Example 1 except that this soft magnetic thermosetting composition was used.
　　比較例１
　（軟磁性熱硬化性フィルム）
　軟磁性熱硬化性組成物に対し軟磁性粒子が４０体積％となるように、軟磁性粒子５００質量部およびエチレン酢酸ビニル共重合体１０６質量部を混合することにより、軟磁性熱硬化性組成物を得た。 Comparative Example 1
(Soft magnetic thermosetting film)
By mixing 500 parts by weight of soft magnetic particles and 106 parts by weight of ethylene vinyl acetate copolymer so that the soft magnetic particles are 40% by volume with respect to the soft magnetic thermosetting composition, the soft magnetic thermosetting composition is mixed. Got.
　この軟磁性熱硬化性組成物をトルエンに溶解させることにより、固形分濃度４０質量％の軟磁性熱硬化性組成物溶液を調製した。 This soft magnetic thermosetting composition was dissolved in toluene to prepare a soft magnetic thermosetting composition solution having a solid concentration of 40% by mass.
　この軟磁性熱硬化性組成物溶液を、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からなるセパレータ（平均厚みが５０μｍ）上に塗布し、その後、１３０℃で２分間乾燥させた。 This soft magnetic thermosetting composition solution was applied onto a separator (average thickness: 50 μm) made of a polyethylene terephthalate film subjected to silicone release treatment, and then dried at 130 ° C. for 2 minutes.
　これにより、セパレータが積層された軟磁性熱硬化性フィルム（軟磁性熱硬化性フィルムのみの平均厚み、９０μｍ）を製造した。 Thereby, a soft magnetic thermosetting film (average thickness of only the soft magnetic thermosetting film, 90 μm) on which the separator was laminated was manufactured.
　（軟磁性フィルム）
　次いで、この軟磁性熱硬化性フィルムを、４層積層し、１７５℃、３０分、２０ＭＰａの条件で熱プレスにより加熱硬化させることにより、比較例１の軟磁性フィルムを作製した。 (Soft magnetic film)
Next, four layers of this soft magnetic thermosetting film were laminated and heat-cured by hot pressing under the conditions of 175 ° C., 30 minutes, 20 MPa, to produce the soft magnetic film of Comparative Example 1.
　　比較例２および３
　表１に記載の材料および配合割合で、軟磁性熱硬化性組成物を得た。この軟磁性熱硬化性組成物を用いた以外は、実施例１と同様にして、比較例２および３の軟磁性熱硬化性フィルムおよび軟磁性フィルムを製造した。 Comparative Examples 2 and 3
Soft magnetic thermosetting compositions were obtained with the materials and blending ratios shown in Table 1. A soft magnetic thermosetting film and a soft magnetic film of Comparative Examples 2 and 3 were produced in the same manner as in Example 1 except that this soft magnetic thermosetting composition was used.
　（初期比透磁率（μ０´）の測定）
　各実施例および各比較例にて製造した軟磁性フィルムについて、熱プレスした直後（３０分後）の時点での比透磁率を、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）によって測定した。これを初期比透磁率（μ０´）とした。その結果を表１に示す。 (Measurement of initial relative permeability (μ0 '))
About the soft magnetic film manufactured in each Example and each comparative example, the relative magnetic permeability at the time immediately after hot pressing (after 30 minutes) was measured using an impedance analyzer (manufactured by Agilent, “4294A”). It was measured by the turn method (frequency 1 MHz). This was set as the initial relative permeability (μ0 ′). The results are shown in Table 1.
　（比透磁率（μ１´）の測定）
　各実施例および各比較例にて製造した軟磁性フィルムについて、初期比透磁率の測定を実施した後、８５℃８５％ＲＨの雰囲気下に、１６８時間保存した。この１６８時間保存時点の軟磁性フィルムの比透磁率を、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）によって測定した。これを比透磁率（μ１´）とした。その結果を表１に示す。 (Measurement of relative permeability (μ1 '))
The soft magnetic films produced in each Example and each Comparative Example were measured for initial relative magnetic permeability and then stored for 168 hours in an atmosphere of 85 ° C. and 85% RH. The relative magnetic permeability of the soft magnetic film when stored for 168 hours was measured by a one-turn method (frequency 1 MHz) using an impedance analyzer (manufactured by Agilent, “4294A”). This was defined as the relative permeability (μ1 ′). The results are shown in Table 1.
　（高温高湿下長期保存後の比透磁率）
　比透磁率（μ１´）の測定を実施した後、次いで、８５℃８５％ＲＨの雰囲気下で４００時間経過時点および７００時間経過時点の比透磁率μ´についても、上記と同様にして測定した。その結果を表１に示す。 (Relative permeability after long-term storage under high temperature and high humidity)
After measuring the relative magnetic permeability (μ1 ′), the relative magnetic permeability μ ′ at the time of 400 hours and at the time of 700 hours was then measured in the same manner as described above in an atmosphere of 85 ° C. and 85% RH. . The results are shown in Table 1.
　表１から明らかなように、実施例１～４の軟磁性フィルムは、４００時間や７００時間経過後においても、軟磁性フィルムを製造した時点の初期比透磁率を基準にして、高い割合の比透磁率を備えていた、すなわち、比透磁率の低下が抑制されていた。一方、比較例１～３の軟磁性フィルムでは、４００時間や７００時間経過後では、軟磁性フィルムを製造した時点の初期比透磁率を基準にして、比透磁率が大きく低下していた。また、比較例２および比較例３の軟磁性フィルムでは、４００～７００時間で比透磁率の低下が進行していた。 As is apparent from Table 1, the soft magnetic films of Examples 1 to 4 have a high ratio of the ratio based on the initial relative permeability at the time when the soft magnetic film was produced even after 400 hours or 700 hours. The magnetic permeability was provided, that is, the decrease in the relative magnetic permeability was suppressed. On the other hand, in the soft magnetic films of Comparative Examples 1 to 3, after 400 hours or 700 hours, the relative magnetic permeability was greatly reduced with reference to the initial relative magnetic permeability at the time of producing the soft magnetic film. Further, in the soft magnetic films of Comparative Example 2 and Comparative Example 3, the decrease in the relative magnetic permeability proceeded in 400 to 700 hours.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　表における各成分中の数値は、特段の記載がない場合には、質量部を示す。また、表中、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「ＳＰ－７」、軟磁性粒子、扁平状、平均粒子径６５μｍ、メイト社製
・アクリル酸エステル系ポリマー：商品名「パラクロンＷ－１９７ＣＭ」、アクリル酸エチル－メタクリル酸メチルを主成分とするアクリル酸エステル系ポリマー、根上工業社製
・ビスフェノールＡ型エポキシ樹脂：商品名「エピコート１００４」、エポキシ当量８７５～９７５ｇ／ｅｑ、ＪＥＲ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１８０～１９０ｇ／ｅｑ、ＪＥＲ社製
・４官能アミノグリシジル型エポキシ樹脂：商品名「テトラッド－Ｃ」、エポキシ当量１０５ｇ／ｅｑ、、三菱瓦斯化学工業社製
・フェノールアラルキル樹脂：商品名「ミレックスＸＬＣ－４Ｌ」、水酸基当量１７０ｇ／ｅｑ、三井化学社製
・２－フェニル－４，５－ジヒドロキシメチルイミダゾール：熱硬化触媒、商品名「キュアゾール２ＰＨＺ－ＰＷ」、四国化成社製
・ポリエーテルリン酸エステル：分散剤、商品名「ＨＩＰＬＡＡＤ　ＥＤ１５２」、楠本化成社製、酸価２０
・エチレン酢酸ビニル共重合体：商品名「ＥＶ１７０」、三井デュポンポリケミカル社製
　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。 The numerical value in each component in a table | surface shows a mass part, when there is no special description. Details of the abbreviations of each component in the table are described below.
-Fe-Si-Al alloy: Trade name "SP-7", soft magnetic particles, flat, average particle size 65 µm, manufactured by Mate, Inc.-Acrylic acid ester polymer: Trade name "Paracron W-197CM", ethyl acrylate -Acrylic acid ester polymer based on methyl methacrylate, manufactured by Negami Kogyo Co., Ltd., bisphenol A type epoxy resin: Trade name "Epicoat 1004", epoxy equivalent of 875-975 g / eq, JER Co., Ltd., bisphenol A type epoxy resin : Trade name “Epicoat YL980”, epoxy equivalent 180-190 g / eq, manufactured by JER ・ Tetrafunctional aminoglycidyl type epoxy resin: Trade name “Tetrad-C”, epoxy equivalent 105 g / eq, manufactured by Mitsubishi Gas Chemical Industries, Ltd. Phenol aralkyl resin: Trade name “Mirex XLC-4L”, hydroxyl equivalent 1 0 g / eq, Mitsui Chemicals Co., Ltd. 2-Phenyl-4,5-dihydroxymethylimidazole: thermosetting catalyst, trade name “Curazole 2PHZ-PW”, Shikoku Kasei Co., Ltd., polyether phosphate ester: dispersant, trade name “HIPLAAD ED152”, manufactured by Enomoto Kasei Co., Ltd., acid value 20
-Ethylene vinyl acetate copolymer: trade name "EV170", manufactured by Mitsui DuPont Polychemical Co., Ltd. Although the above invention is provided as an exemplary embodiment of the present invention, this is merely an example and is limitedly interpreted. should not be done. Variations of the present invention that are apparent to one of ordinary skill in the art are within the scope of the following claims.
　本発明の軟磁性熱硬化性フィルムおよび軟磁性フィルムは、各種の工業製品に適用することができ、例えば、デジタイザなどの位置検出装置などに用いることができる。 The soft magnetic thermosetting film and soft magnetic film of the present invention can be applied to various industrial products, and can be used, for example, for position detection devices such as digitizers.

Claims (4)

  1. 　軟磁性粒子を含有する軟磁性熱硬化性フィルムであって、
    　前記軟磁性熱硬化性フィルムを加熱硬化した直後の周波数１ＭＨｚにおける初期比透磁率μ０´と、前記軟磁性熱硬化性フィルムを加熱硬化し、８５℃、８５％ＲＨの雰囲気下で１６８時間放置したときの周波数１ＭＨｚにおける比透磁率μ１´との比率（μ１´／μ０´）が０．８５以上であることを特徴とする、軟磁性熱硬化性フィルム。　     A soft magnetic thermosetting film containing soft magnetic particles,
    The initial relative magnetic permeability μ0 ′ at a frequency of 1 MHz immediately after heat-curing the soft magnetic thermosetting film and the soft magnetic thermosetting film were heat-cured and left in an atmosphere of 85 ° C. and 85% RH for 168 hours. A soft magnetic thermosetting film characterized in that a ratio (μ1 ′ / μ0 ′) to a relative permeability μ1 ′ at a frequency of 1 MHz is 0.85 or more.
  2. 　前記軟磁性粒子を４０体積％以上含有する軟磁性熱硬化性組成物から形成されることを特徴とする、請求項１に記載の軟磁性熱硬化性フィルム。 The soft magnetic thermosetting film according to claim 1, wherein the soft magnetic thermosetting film is formed from a soft magnetic thermosetting composition containing 40% by volume or more of the soft magnetic particles.
  3. 　前記軟磁性熱硬化性組成物が、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することを特徴とする、請求項２に記載の軟磁性熱硬化性フィルム。 The soft magnetic thermosetting film according to claim 2, wherein the soft magnetic thermosetting composition contains an epoxy resin, a phenol resin, and an acrylic resin.
  4. 　軟磁性熱硬化性フィルムを加熱硬化し、硬化状態にすることにより得られる軟磁性フィルムであって、
    　前記軟磁性熱硬化性フィルムは、軟磁性粒子を含有し、
    前記軟磁性熱硬化性フィルムを加熱硬化した直後の周波数１ＭＨｚにおける初期比透磁率μ０´と、前記軟磁性熱硬化性フィルムを加熱硬化し、８５℃、８５％ＲＨの雰囲気下で１６８時間放置したときの周波数１ＭＨｚにおける比透磁率μ１´との比率（μ１´／μ０´）が０．８５以上であることを特徴とする、軟磁性フィルム。     A soft magnetic film obtained by heat-curing a soft magnetic thermosetting film to obtain a cured state,
    The soft magnetic thermosetting film contains soft magnetic particles,
    The initial relative magnetic permeability μ0 ′ at a frequency of 1 MHz immediately after heat-curing the soft magnetic thermosetting film and the soft magnetic thermosetting film were heat-cured and left in an atmosphere of 85 ° C. and 85% RH for 168 hours. A soft magnetic film having a ratio (μ1 ′ / μ0 ′) to a relative permeability μ1 ′ at a frequency of 1 MHz of 0.85 or more.
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