TW201435931A - Soft magnetic thermosetting film and soft magnetic film - Google Patents

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 DEG C, 85% RH atmosphere is at least 0.85.

Description

Soft magnetic thermosetting film and soft magnetic film

The present invention relates to a soft magnetic thermosetting film and a soft magnetic film obtained therefrom.

A position detecting device that moves a pen type position indicator on a position detecting plane to detect a position is called a digitizer, and is popular as an input device of a computer. The position detecting device includes a position detecting plane plate and a circuit board (sensor substrate) disposed below the substrate and having a loop coil formed on the surface of the substrate. And, the position of the position indicator is detected by utilizing electromagnetic induction generated by the position indicator and the loop coil.

In order to improve the communication efficiency in order to control the magnetic flux generated when the electromagnetic induction is applied to the position detecting device, it is proposed to arrange a soft magnetic film containing a soft magnetic substance on the surface (opposite side) of the sensor substrate opposite to the position detecting plane. The method (for example, refer to Patent Document 1).

Patent Document 1 discloses a soft magnetic film containing a soft magnetic powder, a binder resin including an acrylic rubber, a phenol resin, an epoxy resin, and melamine, and a metal phosphonate salt. The soft magnetic film contains a metal phosphonic acid salt or melamine at a high ratio, thereby imparting flame retardancy to the circuit substrate without affecting the reliability of the electronic device.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2012-212790

Moreover, the soft magnetic film is usually made by containing a soft magnetic powder and a binder resin. The thermosetting resin is produced by heat curing. However, if the soft magnetic film is stored for a long period of time in a high-temperature and high-humidity environment after heating, the magnetic properties such as relative magnetic permeability may be deteriorated.

An object of the present invention is to provide a soft magnetic thermosetting film which can suppress deterioration of magnetic properties even after storage for a long period of time in a high-temperature and high-humidity environment, and a soft magnetic film obtained therefrom.

The soft magnetic thermosetting film of the present invention is characterized in that it contains soft magnetic particles, and the initial relative magnetic permeability μ0' at a frequency of 1 MHz immediately after heat-hardening the soft magnetic thermosetting film and the soft magnetic thermosetting film are heated. The ratio (μ1'/μ0') of the relative magnetic permeability μ1' at a frequency of 1 MHz when it was hardened and left in an environment of 85 ° C and 85% RH (Relative Humidity) was 0.85 or more.

Moreover, it is preferable that the soft magnetic thermosetting film of the present invention is formed of a soft magnetic thermosetting composition containing 40% by volume or more of the soft magnetic particles.

Further, 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.

Moreover, the soft magnetic film of the present invention is obtained by heating and hardening the soft magnetic thermosetting film to a hardened state.

The soft magnetic film of the present invention obtained by heat-hardening the soft magnetic thermosetting film of the present invention can suppress deterioration of magnetic properties even after being stored (placed) for a long period of time in a high-temperature and high-humidity environment, and has excellent magnetic properties.

The soft magnetic thermosetting film of the present invention is formed, for example, of a soft magnetic thermosetting composition containing soft magnetic particles and a resin component.

Examples of the soft magnetic material constituting the soft magnetic particles include magnetic stainless steel. (Fe-Cr-Al-Si alloy), Standust (Fe-Si-Al alloy), Permalloy (Fe-Ni alloy), beryllium 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, ferrite Wait. Among these, a tridext alloy (Fe-Si-Al alloy) is preferably exemplified in terms of magnetic properties.

Among these, an Fe-Si-Al alloy having a Si content ratio of 9 to 15% by mass can be more preferably exemplified. Thereby, the magnetic properties 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 is, for example, 80 or less, preferably 65 or less. The flatness ratio can be 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 μm or more, preferably 10 μm or more, and is, for example, 100 μm or less. The average thickness is, for example, 0.3 μm or more, preferably 0.5 μm or more, and is, for example, 3 μm or less, or preferably 2.5 μm or less. By adjusting the flatness ratio, the average particle diameter, the average thickness, and the like of the soft magnetic particles, the influence of the demagnetizing field by the soft magnetic particles can be reduced, and as a result, the magnetic permeability of the soft magnetic particles can be increased. Further, in order to make the size of the soft magnetic particles uniform, it is also possible to use soft magnetic particles classified by a sieve or the like as needed.

The mass ratio of the soft magnetic particles in the soft magnetic thermosetting composition (further, the soft magnetic thermosetting film or the soft magnetic film) is, for example, 70% by mass or more, preferably 80% by mass or more, and more preferably 85% by mass or more. Further, 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 further, for example, 80% by volume or less, preferably 70% by volume. % or less, more preferably 60% by volume or less. The soft magnetic film is excellent in moldability by setting it as the range of the said upper limit or less. On the other hand, the soft magnetic film is made to have a range equal to or higher than the above lower limit. Excellent magnetic properties.

The resin component contains a thermosetting resin.

Examples of the thermosetting resin include an epoxy resin, a phenol resin, an amine resin, an unsaturated polyester resin, a polyurethane resin, a polyoxyl resin, a urea resin, a melamine resin, and a thermosetting polyimide resin. Diallyl phthalate resin and the like. An epoxy resin or a phenol resin is preferably used, and a combination of an epoxy resin and a phenol resin can be more preferably used. These may 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, and examples thereof include a bisphenol type epoxy resin (especially a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, and a bisphenol). S-type epoxy resin, brominated bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, bisphenol AF epoxy resin, etc.), phenolic epoxy resin (especially phenol novolak epoxy resin) , o-cresol novolak type epoxy resin, etc.), biphenyl type epoxy resin, naphthalene type epoxy resin, fluorene type epoxy resin, trishydroxyphenylmethane type epoxy resin, tetraphenol ethane type epoxy A difunctional epoxy resin such as a resin or a polyfunctional epoxy resin. Further, for example, an intramethylene urethane type epoxy resin, a isocyanuric acid triglycidyl type epoxy resin, a glycidylamine type epoxy resin, or the like may be mentioned. These may be used alone or in combination of two or more.

Among these epoxy resins, preferred are bisphenol type epoxy resins, novolac type epoxy resins, o-cresol novolak type epoxy resins, biphenyl type epoxy resins, and trihydroxyphenylmethane. A bisphenol type epoxy resin can be more preferably exemplified as the resin or the tetraphenol ethane type epoxy resin. By containing these epoxy resins, the reactivity with the phenol resin is excellent, and as a result, the soft magnetic film obtained by heat-hardening the soft magnetic thermosetting film is excellent in long-term storage property in magnetic properties in a high-temperature and high-humidity environment.

The phenol resin is a curing agent for an epoxy resin, and examples thereof include a phenol novolak resin, a phenol aralkyl resin, a cresol novolak resin, a third butyl phenol novolak resin, and a nonylphenol novolak resin. A phenol resin such as a resol type phenol resin such as polyhydroxystyrene such as polyparaxyl styrene. These can be used alone or in combination 2 or more types. Among these phenol resins, a novolak type resin is preferably exemplified, and a phenol novolak resin or a phenol aralkyl resin can be more preferably exemplified, and a phenol aralkyl resin can be further preferably exemplified. By containing these phenol resins, the reactivity with an epoxy resin is excellent, and as a result, the soft magnetic film is excellent in long-term storage property.

When the epoxy resin and the phenol resin are used in combination with the resin component, when the hydroxyl equivalent of the phenol resin is 1 g/eq or more and less than 100 g/eq with respect to the epoxy equivalent of the epoxy resin of 100 g/eq, the epoxy resin is relative to the epoxy resin. The content ratio of the resin component is, for example, 15 parts by mass or more, preferably 30 parts by mass or more, and is, for example, 70 parts by mass or less, preferably 50 parts by mass or less, more preferably 40 parts by mass or less, of phenol. The content ratio of the resin to 100 parts by mass of the resin component is, for example, 5 parts by mass or more, preferably 15 parts by mass or more, and for example, 30 parts by mass or less, preferably 20 parts by mass or less.

When the hydroxyl equivalent of the phenol resin is 100 g/eq or more and less than 200 g/eq with respect to the epoxy equivalent 100 g/eq of the epoxy resin, the content ratio of the epoxy resin to 100 parts by mass of the resin component is, for example, 10 mass. The content 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, more preferably 25 parts by mass or more, and further preferably 25 parts by mass or more. For example, it is 50 mass parts or less.

When the hydroxyl equivalent of the phenol resin is 200 g/eq or more and 1000 g/eq or less with respect to the epoxy equivalent 100 g/eq of the epoxy resin, the content ratio of the epoxy resin to 100 parts by mass of the resin component is, for example, 5 parts by mass. 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, and more preferably, for example, 15 parts by mass or more. It is 70 parts by mass or less.

Furthermore, the epoxy equivalent of the two epoxy resins is used to multiply the epoxy equivalent of each epoxy resin by the mass ratio of each epoxy resin to the total amount of the epoxy resin, and then add them together. Epoxy equivalent of all epoxy resins.

In addition, the hydroxyl group equivalent in the phenol resin is, for example, 0.2 equivalent or more, preferably 0.5 equivalent or more, and further preferably 2.0 equivalents or less, and preferably 1.2 equivalents or less, per equivalent of the epoxy group of the epoxy resin. When the amount of the hydroxyl group is within the above range, the hardening 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. Further preferably, the resin component is composed only of an epoxy resin, a phenol resin, and an acrylic resin. When a soft magnetic film is produced by laminating a plurality of layers of a soft magnetic thermosetting film and heat-pressing a resin layer, the soft magnetic film having uniform unevenness at the laminated interface and excellent magnetic properties can be obtained. .

The acrylic resin is, for example, acrylic acid obtained by polymerizing one or two or more kinds of alkyl (meth)acrylates having a linear or branched alkyl group as a monomer component and polymerizing the monomer component. It is a polymer or the like. Further, "(meth)acrylic acid (醯)" means "acrylic acid (醯) and/or methacrylic acid (醯)".

Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a n-butyl group, a tert-butyl group, an isobutyl group, a pentyl group, an isopentyl group, a hexyl group, a heptyl group, a cyclohexyl group, and 2 -ethylhexyl, octyl, isooctyl, decyl, isodecyl, decyl, isodecyl, undecyl, lauryl, tridecyl, tetradecyl, stearyl, octadecyl An alkyl group such as an alkyl group or a dodecyl group having 1 to 20 carbon atoms. An alkyl group having 1 to 6 carbon atoms is preferred.

The acrylic polymer may also be a copolymer of an alkyl (meth)acrylate and another monomer.

Examples of the other monomer include glycidyl group-containing monomers such as glycidyl acrylate and glycidyl methacrylate, such as acrylic acid, methacrylic acid, carboxyethyl acrylate, carboxy amyl acrylate, and itaconic acid. a carboxyl group-containing monomer such as maleic acid, fumaric acid or crotonic acid, for example, an acid anhydride monomer such as maleic anhydride or itaconic anhydride, for example, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, a hydroxyl group-containing monomer such as 10-hydroxydecyl (meth)acrylate, 12-hydroxylauryl (meth)acrylate or (4-hydroxymethylcyclohexyl)-methyl acrylate, such as styrenesulfonic acid or allylic acid Sulfonic acid, 2-(methyl) propylene decylamine-2-methylpropane sulfonic acid, (meth) acrylamide propyl sulfonic acid, sulfopropyl (meth) acrylate, (meth) propylene oxime A sulfonic acid group-containing monomer such as a naphthalenesulfonic acid or a phosphoric acid group-containing monomer such as 2-hydroxyethyl acrylate or a hydroxy group such as styrene monomer or acrylonitrile.

Among these, a glycidyl group-containing monomer, a carboxyl group-containing monomer or a hydroxyl group-containing monomer can be preferably exemplified. When the acrylic resin is a copolymer of an alkyl (meth)acrylate and a monomer other than the above, that is, when the acrylic resin has a glycidyl group, a carboxyl group or a hydroxyl group, the soft magnetic film is resistant to back. Better weldability.

In the case of a copolymer of an alkyl (meth) acrylate and another monomer, the compounding ratio (mass) of the other monomer is preferably 40% by mass or less based on 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 of the soft magnetic thermosetting film and the reflow resistance. Further, the weight average molecular weight can be measured by gel permeation chromatography (GPC) using a standard polystyrene equivalent value.

The glass transition point (Tg) of the acrylic resin is, for example, -30 ° C or higher, preferably -20 ° C or higher, and is, for example, 30 ° C or lower, preferably 15 ° C or lower. When it is at least the above lower limit, the soft magnetic thermosetting film is excellent in adhesion. On the other hand, when it is less than or equal to the above upper limit, the soft magnetic thermosetting film is excellent in handleability. Furthermore, the glass transition point can be measured by a dynamic viscoelasticity measuring device (DMA (Dynamic Mechanical Analyzer), frequency 1 Hz, heating rate 10 ° C / min) to measure the maximum value of the loss tangent (tan δ) And get.

When the resin component contains an acrylic resin, the content ratio of the thermosetting resin in the resin component is, for example, 35 mass% or more, preferably 50 mass% or more, more preferably 52 mass% or more. Further, for example, it is 90% by mass or less, preferably 80% by mass or less, more Preferably, it is 60% by mass or less. When the content ratio of the thermosetting resin is in the above range, particularly in the case of enriching the thermosetting resin (more than 50% by mass), the expansion of the resin due to water absorption or heat, and the void of the soft magnetic film can be effectively suppressed. When it is produced, the magnetic properties in a high-temperature and high-humidity environment are excellent in long-term storage properties.

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 less than 50% by mass. More preferably, it is 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 further, for example, 30% by mass or less, preferably 20% by mass. Hereinafter, it is more preferably 15% by mass or less. By setting it as the said range, it is excellent in the film-forming property and magnetic characteristics of a soft magnetic film.

In addition, the content ratio of the thermosetting resin (preferably a thermosetting resin containing an epoxy resin and a phenol resin) is 100 parts by mass, for example, 20 parts of the soft magnetic particle-excluding component other than the soft magnetic particles in the soft magnetic thermosetting composition. The mass part or more is preferably 30 parts by mass or more, more preferably 40 parts by mass or more, further preferably more than 50 parts by mass, most preferably 52 parts by mass or more, and further, for example, 99 parts by mass or less, preferably 90%. The amount by mass or less is more preferably 80 parts by mass or less, further preferably 70 parts by mass or less, and most preferably 60 parts by mass or less. By setting it as the said range, the soft magnetic film is excellent in the long-term storage property of the magnetic characteristics in the high temperature and high humidity environment.

More specifically, the soft magnetic particle-excluding component contains a component of a resin component, a thermosetting catalyst (described below) and an additive (described below) which are optionally added, and does not contain soft magnetic particles and a solvent.

The resin component may contain a thermoplastic resin other than a thermosetting resin or an acrylic resin.

Examples of such a thermoplastic resin include natural rubber, butyl rubber, isoprene rubber, chloroprene rubber, ethylene-vinyl acetate copolymer, copolymer, and poly Butadiene resin, polycarbonate resin, thermoplastic polyimide resin, polyamide resin (6-nylon, 6,6-nylon, etc.), phenoxy resin, saturated polyester resin (PET (polyethylene terephthalate) Ethylene terephthalate), PBT (polybutylene terephthalate (polybutylene terephthalate), etc.), polyamidoximine resin, fluororesin, and the like. These resins may be used alone or in combination of two or more.

The soft magnetic thermosetting composition preferably contains a thermosetting catalyst.

The thermosetting catalyst is not limited as long as it is a catalyst for promoting the curing of the resin component by heating, and examples thereof include a salt having an imidazole skeleton, a salt having a triphenylphosphine structure, and triphenylboron. a salt of an alkane structure, a compound containing an amine group, and the like. A salt having an imidazole skeleton can be preferably exemplified.

Examples of the salt having an imidazole skeleton include 2-phenylimidazole (trade name: 2PZ), 2-ethyl-4-methylimidazole (trade name: 2E4MZ), and 2-methylimidazole (trade name: 2MZ). ), 2-undecylimidazole (trade name: C11Z), 2-phenyl-4,5-dihydroxymethylimidazole (trade name: 2PHZ-PW), 2,4-diamino-6-( 2'-Methylimidazolyl (1)') Ethyl . An isocyanurate adduct (trade name: 2MAOK-PW), etc. (the above-mentioned trade names are all manufactured by Shikoku Chemicals Co., Ltd.). The heat-curing catalyst may be used singly or in combination of two or more.

Examples of the shape of the heat-curing catalyst include a spherical shape, an ellipsoid shape, and the like.

The blending ratio of the heat-hardening catalyst is, for example, 0.1 parts by mass or more, preferably 0.3 parts by mass or more, and further, for example, 5 parts by mass or less, preferably 3 parts by mass or less, based on 100 parts by mass of the resin component. By setting the blending ratio of the heat-hardening catalyst within the above range, the soft magnetic thermosetting film can be heat-hardened at a relatively low temperature and for a short period of time, and the long-term storage property and reflow resistance of the magnetic properties in a high-temperature and high-humidity environment can be achieved. Excellent.

The soft magnetic thermosetting composition (further, the soft magnetic thermosetting film and the soft magnetic film) may optionally contain a commercially available or well-known additive such as a dispersing agent, a crosslinking agent, or an inorganic filler.

The soft magnetic thermosetting composition preferably contains a dispersing agent.

Examples of the dispersant include a polyether phosphate, a decane coupling agent, and a titanate coupling agent. A polyether phosphate ester is preferably exemplified. By allowing the soft magnetic thermosetting composition to contain a dispersing agent, particularly a polyether phosphate, the coating property of the soft magnetic thermosetting composition can be improved, and the magnetic properties of the soft magnetic film can be further improved.

Examples of the polyether phosphates include polyoxyalkylene alkyl alkyl ether phosphates and polyoxyalkylene alkylphenyl ether phosphates. A polyoxyalkylene alkyl ether phosphate can be preferably exemplified.

The polyoxyalkylene alkyl ether phosphate has a form in which 1 to 3 alkyl-oxy-poly(alkylene oxide) groups are bonded to a phosphorus atom of a phosphate. In the alkyl-oxy-poly(alkylene oxide) group [that is, the polyoxyalkylene alkyl ether moiety], the number of repetitions of the alkoxy group as the poly(alkylene oxide) moiety is not particularly limited. For example, it can be appropriately selected from the range of 2 to 30 (preferably 3 to 20). The alkylene group having a poly(alkylene oxide) moiety is preferably an alkylene group having a carbon number of 2 to 4. Specific examples thereof include an ethyl group, a propyl group, an extended isopropyl group, a butyl group, an isobutyl group and the like. Further, the alkyl group is not particularly limited, and examples thereof include an alkyl group having 6 to 30 carbon atoms, and more preferably an alkyl group having 8 to 20 carbon atoms. Specifically, examples of the alkyl group include a mercapto group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, and a heptadecyl group. Octadecyl and the like. Further, in the case where the polyoxyalkylene alkyl ether phosphate has a plurality of alkyl-oxy-poly(alkylene oxide) groups, the plurality of alkyl groups may be different or the same. Further, the polyether phosphate may also be a mixture with an amine or the like.

The acid value of the polyether phosphate is, for example, 10 or more, preferably 15 or more, and is, for example, 200 or less, preferably 150 or less. The acid value can be measured by a neutralization titration method or the like.

Examples of the decane coupling agent include 3-methacryloxypropyltrimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, and the like.

The dispersing agent may be used singly or in combination of two or more.

Specific examples of the dispersing agent include the HIPLAAD series ("ED152", "ED153", "ED154", "ED118", "ED174") of Nanben Chemical Co., Ltd. "ED251"), KBM series ("KBM303", "KBM503") manufactured by Shin-Etsu Chemical Co., Ltd., etc.

The content ratio of the dispersing agent is, for example, 0.1 part by mass or more, preferably 0.2 part by mass or more, based on 100 parts by mass of the soft magnetic particles. Further, for example, it is 5 parts by mass or less, preferably 2 parts by mass or less.

The soft magnetic thermosetting composition can be prepared by mixing the above components in the above-mentioned content ratio.

Next, a method of producing the soft magnetic thermosetting film of the present invention will be described.

In the production of the soft magnetic thermosetting film, a soft magnetic thermosetting composition solution obtained by dissolving or dispersing the soft magnetic thermosetting composition in a solvent is prepared.

The solvent may, for example, be a ketone such as acetone or methyl ethyl ketone (MEK), or an ester such as ethyl acetate, or an ether such as propylene glycol monomethyl ether, for example, N,N-dimethylformamide or the like. An organic solvent such as guanamine. Further, examples of the solvent include water, for example, an aqueous solvent such as an alcohol such as methanol, ethanol, propanol or isopropanol.

The amount of the solid content component in the soft magnetic thermosetting composition solution is, for example, 10% by mass or more, preferably 30% by mass or more, and further, for example, 90% by mass or less, preferably 70% by mass or less.

Next, the soft magnetic thermosetting composition solution is applied onto the surface of a release substrate (separator, core material, etc.) and dried. Thereby, a soft magnetic thermosetting film can be obtained.

The coating 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 higher and 160° C. or lower, and the drying time is, for example, 1 minute or longer and 5 minutes or shorter.

Examples of the separator include a polyethylene terephthalate (PET) film, a polyethylene film, a polypropylene film, and paper. The surface of the separator is subjected to a release treatment by, for example, a fluorine-based release agent, an acrylic long-chain alkyl ester release agent, a polyoxymethylene release agent, or the like.

Examples of the core material include a plastic film (for example, a polyimide film, a polyester film, a polyethylene terephthalate film, a polyethylene naphthalate film, a polycarbonate film, etc.), and a metal film. (for example, aluminum foil, etc.), for example, a resin substrate reinforced by a glass fiber or a non-woven fabric made of plastic, a ruthenium substrate, a glass substrate, or the like.

The average thickness of the separator or the core material is, for example, 1 μm or more and 500 μm or less.

Thereby, a soft magnetic thermosetting film was obtained.

The soft magnetic thermosetting film is a soft magnetic thermosetting adhesive film having a semi-hardened state (B-stage state) at room temperature (specifically, 25 ° C) and having good adhesion.

Further, the soft magnetic thermosetting film preferably contains flat soft magnetic particles, and the flat soft magnetic particles are arranged along the two-dimensional in-plane direction of the soft magnetic thermosetting film. In other words, the longitudinal direction of the flat soft magnetic particles (the direction orthogonal to the thickness direction) is aligned along the surface direction of the soft magnetic thermosetting film. Thereby, the soft magnetic thermosetting film fills the soft magnetic particles at a high ratio and is excellent in magnetic properties. Moreover, thin film formation is achieved.

The average thickness of the soft magnetic thermosetting film is, for example, 5 μm or more, preferably 50 μm or more, and is, for example, 500 μm or less, or preferably 250 μm or less.

The soft magnetic thermosetting film of the present invention can be, for example, a single layer structure composed of a single layer of a soft magnetic thermosetting film, a multilayer structure having a soft magnetic thermosetting film on one side or two layers of a core material, and a soft magnetic thermosetting film. The single-sided or two-area layer has a multilayer structure such as a separator.

Next, the soft magnetic film of the present invention will be described.

The soft magnetic film is formed of the above soft magnetic thermosetting film. Specifically, the soft magnetic film can be obtained by heat-hardening the above soft magnetic thermosetting film.

Preferably, a plurality of soft magnetic thermosetting films are prepared, and a plurality of soft magnetic thermosetting films are subjected to hot pressing in a thickness direction by hot pressing (hot pressing step). Thereby, the soft magnetic particles can be filled into the soft magnetic thermosetting film at a high ratio, thereby improving magnetic properties.

The hot pressing can be carried out using a known press, and for example, a parallel plate press can be cited. Wait.

The number of laminated layers of the soft magnetic thermosetting film is, for example, two or more layers, and is, for example, 20 or less, preferably 5 or less. Thereby, the soft magnetic film can be adjusted to a desired thickness.

The heating temperature is, for example, 80 ° C or higher, preferably 100 ° C or higher, and is, for example, 200 ° C or lower, preferably 180 ° C or lower.

The heating time is, for example, 0.1 hour or longer, preferably 0.2 hour or longer, and for example, 24 hours or shorter, preferably 2 hours or shorter.

The pressure is, for example, 10 MPa or more, preferably 20 MPa or more, and is, for example, 500 MPa or less, preferably 200 MPa or less.

Thereby, the soft magnetic thermosetting film in a semi-hardened state can be heat-hardened to obtain a soft magnetic film in a hardened state (C-stage state).

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.

The relative magnetic permeability (initial relative magnetic permeability μ0') at a frequency of 1 MHz immediately after heat-hardening of the soft magnetic film (specifically, within 30 minutes after heat-hardening the soft magnetic thermosetting film) is, for example, 100 or more. It is preferably 150 or more, more preferably 180 or more, and is, for example, 400 or less.

The relative magnetic permeability (relative magnetic permeability μ1') at a frequency of 1 MHz when left to stand in an environment of 85 ° C and 85% RH after heat curing is, for example, 100 or more, preferably 150 or more, more preferably 180. The above is also, for example, 400 or less.

Further, the ratio (μ1'/μ0') of the initial relative magnetic permeability μ0' to the relative magnetic permeability μ1' is 0.85 or more, preferably 0.90 or more, more preferably 0.95 or more, still more preferably 0.96 or more, and most preferably It is 0.97 or more, and is, for example, 1.00 or less. By setting the above ratio within the above range, the soft magnetic film is excellent in long-term storage property of magnetic properties in a high-temperature and high-humidity environment.

The relative magnetic permeability (μ0' and μ1') can be measured using an Impedance Analyzer ("4294A" manufactured by Agilent, Inc.) by a single coil method (frequency 1 MHz). And measured.

Further, the soft magnetic film is preferably such that the soft magnetic particles contained in the soft magnetic film are arranged along the two-dimensional in-plane direction of the soft magnetic film. In other words, the longitudinal direction of the flat soft magnetic particles (the direction orthogonal to the thickness direction) is aligned along the surface direction of the soft magnetic film. Therefore, the soft magnetic film is a film and is excellent in relative magnetic permeability.

The soft magnetic film can be, for example, a single layer structure composed of only a single layer of a soft magnetic film, a multilayer structure having a soft magnetic film on one side or a two-layer layer of the core material, or a single-sided or two-layer layer on the soft magnetic film. The shape of the multilayer structure of the separator.

Further, in the above embodiment, a plurality of soft magnetic thermosetting films are laminated and hot pressed, but for example, one (single layer) soft magnetic thermosetting film may be subjected to hot pressing.

The soft magnetic film can be preferably used, for example, as a soft magnetic film (magnetic film) for laminating an antenna, a coil, or a circuit board on which the surface is formed. More specifically, it can be used for smart phones, computers, position detection devices, and the like.

In order to laminate a soft magnetic film on a circuit board, a method of fixing a soft magnetic film to a circuit board via an adhesive layer, and directly attaching the soft magnetic thermosetting film to the circuit board, heat-harden the soft magnetic thermosetting film. A method of forming a soft magnetic film and fixing it to a circuit board.

From the viewpoint of miniaturizing the electronic device without the need for the adhesive layer, a method in which the soft magnetic thermosetting film is directly adhered to the circuit board and then the soft magnetic thermosetting film is heat-cured is preferably used.

Moreover, from the viewpoint of insulation, a method of fixing a soft magnetic film to a circuit board via an adhesive layer is preferably exemplified.

The following layer can be used as a binder layer which is generally used as a circuit board, and can be formed, for example, by applying an adhesive such as an epoxy-based adhesive, a polyimide-based adhesive, or an acrylic adhesive, and drying. . The thickness of the subsequent layer is, for example, 10 to 100 μm.

Moreover, the initial relative magnetic permeability μ0' and the relative magnetic permeability μ1' of the soft magnetic thermosetting film The ratio (μ1'/μ0') is 0.85 or more. Therefore, even when the soft magnetic film obtained by heat-hardening the soft magnetic thermosetting film is stored in a high-temperature and high-humidity environment for a long period of time, the soft magnetic property can be suppressed. Deterioration of the relative magnetic permeability of the film. Thereby, excellent magnetic properties can be exhibited for a long period of time.

The temperature resistance in a high-temperature and high-humidity environment is, for example, 50 ° C or higher, preferably 80 ° C or higher, and for example, 150 ° C or lower, preferably 100 ° C or lower.

The humidity resistance in a high-temperature and high-humidity environment is, for example, 50% RH or more, preferably 80% RH or more, and is, for example, 100% RH or less, preferably 90% RH or less.

The storage time in a high-temperature and high-humidity environment is, for example, 96 hours or longer, preferably 168 hours or longer, more preferably 400 hours or longer, and still more preferably 700 hours or longer.

[Examples]

The present invention will be specifically described below by way of examples and comparative examples, but the present invention is not limited to any examples and comparative examples. The numerical values of the examples shown below can be replaced with the numerical values (i.e., the upper limit value or the lower limit value) described in the above embodiments.

Example 1 (soft magnetic thermosetting film)

500 parts by mass of soft magnetic particles, 22 parts by mass of acrylate-based polymer, and bisphenol A-type epoxy resin ("Epikote 1004") 45 mass, so that the soft magnetic particles are 40% by volume with respect to the soft magnetic thermosetting composition. 26 parts by mass of bisphenol A type epoxy resin ("Epikote YL980"), 32 parts by mass of phenol aralkyl resin, and 2-phenyl-4,5-dihydroxymethylimidazole ("2PHZ-PW") 2.16 parts by mass of the catalyst (1.0 parts by mass based on 100 parts by mass of the resin component) and 2.5 parts by mass of the polyether phosphate (dispersant) (0.5 parts by mass based on 100 parts by mass of the soft magnetic particles) are mixed. This gives a soft magnetic thermosetting composition.

A soft magnetic thermosetting composition solution having a solid content concentration of 43% by mass was prepared by dissolving the soft magnetic thermosetting composition in methyl ethyl ketone.

The soft magnetic thermosetting composition solution was applied onto a separator (having an average thickness of 50 μm) containing a polyethylene terephthalate film by polyfluorination-releasing treatment, followed by drying at 130 ° C for 2 minutes.

Thereby, a soft magnetic thermosetting film in which a separator was laminated (only the average thickness of the soft magnetic thermosetting film, 90 μm) was produced.

(soft magnetic film)

Next, the soft magnetic thermosetting film was laminated in four layers and heat-hardened by hot pressing at 175 ° C for 30 minutes and 20 MPa to prepare a soft magnetic film.

Example 2~4

A soft magnetic thermosetting composition was obtained from the materials and the blending ratios shown in Table 1. The soft magnetic thermosetting films and thermosetting films of Examples 2 to 4 were produced in the same manner as in Example 1 except that the soft magnetic thermosetting composition was used.

Comparative example 1 (soft magnetic thermosetting film)

The soft magnetic thermosetting composition was obtained by mixing 500 parts by mass of the soft magnetic particles and 106 parts by mass of the ethylene-vinyl acetate copolymer so that the soft magnetic particles were 40% by volume with respect to the soft magnetic thermosetting composition.

The soft magnetic thermosetting composition was dissolved in toluene, whereby a soft magnetic thermosetting composition solution having a solid content concentration of 40% by mass was prepared.

The soft magnetic thermosetting composition solution was applied onto a separator (having an average thickness of 50 μm) containing a polyethylene terephthalate film by polyfluorination-releasing treatment, followed by drying at 130 ° C for 2 minutes.

Thereby, a soft magnetic thermosetting film in which a separator was laminated (only the average thickness of the soft magnetic thermosetting film, 90 μm) was produced.

(soft magnetic film)

Next, the soft magnetic thermosetting film is laminated in 4 layers at 175 ° C, 30 minutes, 20 The soft magnetic film of Comparative Example 1 was produced by heat-hardening under the conditions of MPa under the conditions of MPa.

Comparative Examples 2 and 3

A soft magnetic thermosetting composition was obtained from the materials and the 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 the soft magnetic thermosetting composition was used.

(Measurement of initial relative magnetic permeability (μ0'))

The soft magnetic film produced in each of the examples and the comparative examples was measured by a single coil method (frequency: 1 MHz) after the hot pressing using an Impedance Analyzer ("4294A" manufactured by Agilent Co., Ltd.). Relative magnetic permeability at the time of 30 minutes). This was set as the initial relative magnetic permeability (μ0'). The results are shown in Table 1.

(Measurement of relative magnetic permeability (μ1'))

The soft magnetic films produced in the respective examples and the comparative examples were subjected to measurement of initial relative magnetic permeability, and then stored in an environment of 85 ° C and 85% RH for 168 hours. The relative magnetic permeability of the soft magnetic film stored at the time of 168 hours was measured by a single coil method (frequency: 1 MHz) using an Impedance Analyzer ("4294A" manufactured by Agilent Co., Ltd.). This is set to the relative magnetic permeability (μ1'). The results are shown in Table 1.

(relative permeability after long-term storage under high temperature and high humidity)

After the relative magnetic permeability (μ1') is measured, the relative magnetic permeability μ' at the time of 400 hours passing through the environment of 85 ° C and 85% RH and the time passing 700 hours is also in the same manner as described above. The measurement was carried out. The results are shown in Table 1.

As is clear from Table 1, the soft magnetic films of Examples 1 to 4 have a relatively high ratio of relative magnetic permeability even after 400 hours or 700 hours, at the initial relative magnetic permeability at the time of producing the soft magnetic film. The decrease in the conductivity, that is, the relative magnetic permeability, is suppressed. On the other hand, in the soft magnetic films of Comparative Examples 1 to 3, the relative magnetic permeability at the time of the production of the soft magnetic film was greatly lowered after 400 hours or 700 hours. Further, in the soft magnetic films of Comparative Example 2 and Comparative Example 3, the relative magnetic permeability was lowered in 400 to 700 hours.

The numerical values in the respective components in the table indicate the parts by mass unless otherwise specified. In addition, the details of the abbreviations of the components in the table are described below.

. Fe-Si-Al alloy: trade name "SP-7", soft magnetic particles, flat shape, average particle size 65μm, manufactured by Meito

. Acrylate-based polymer: trade name "Pagoclone W-197CM", acrylate-based polymer containing ethyl acrylate-methyl methacrylate as main component, manufactured by Kokusai Industrial Co., Ltd.

. Bisphenol A type epoxy resin: trade name "Epikote 1004", epoxy equivalent 875~975g/eq, manufactured by JER

. Bisphenol A type epoxy resin: trade name "Epikote YL980", epoxy equivalent 180~190g/eq, manufactured by JER

. 4-functional aminoglycidyl epoxy resin: trade name "Tetrad-C", epoxy equivalent 105g/eq, manufactured by Mitsubishi Gas Chemical Industry Co., Ltd.

. Phenol aralkyl resin: trade name "Milex XLC-4L", hydroxyl equivalent 170g / eq, manufactured by Mitsui Chemicals Co., Ltd.

. 2-Phenyl-4,5-dihydroxymethylimidazole: thermosetting catalyst, trade name "Curezol 2PHZ-PW", manufactured by Shikoku Chemicals Co., Ltd.

. Polyether phosphate: dispersant, trade name "HIPLAAD ED152", manufactured by Nanben Chemical Company, acid value 20

. Ethylene-vinyl acetate copolymer: trade name "EV170", manufactured by Mitsui-Dupont Polychemical

Further, the invention is provided by the exemplified embodiments of the invention, but is merely illustrative and not to be construed as limiting. Variations of the invention as clarified by those skilled in the art are included in the scope of the following claims.

[Industrial availability]

The soft magnetic thermosetting film and the soft magnetic film of the invention can be applied to various industrial products. For example, it can be used for a position detecting device such as a coordinate reading device.

Claims (4)

A soft magnetic thermosetting film characterized in that it contains soft magnetic particles, and the initial relative magnetic permeability μ0' at a frequency of 1 MHz immediately after heat-hardening the soft magnetic thermosetting film and heat-hardening the soft magnetic thermosetting film The ratio (μ1'/μ0') of the relative magnetic permeability μ1' at a frequency of 1 MHz when placed at 85 ° C and 85% RH for 168 hours was 0.85 or more. The soft magnetic thermosetting film of claim 1, which is formed of a soft magnetic thermosetting composition containing 40% by volume or more of the above soft magnetic particles. 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. A soft magnetic film obtained by heating and hardening a soft magnetic thermosetting film to obtain a hardened state, wherein the soft magnetic thermosetting film contains soft magnetic particles, and the soft magnetic thermosetting film is just heat-hardened. The initial relative magnetic permeability μ0' at a frequency of 1 MHz and the relative magnetic permeability μ1' at a frequency of 1 MHz when the soft magnetic thermosetting film is heat-hardened and left in an environment of 85 ° C and 85% RH for 168 hours. The ratio (μ1'/μ0') is 0.85 or more.