WO2020203924A1 - Resin composition including magnetic powder - Google Patents

Resin composition including magnetic powder Download PDF

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Publication number
WO2020203924A1
WO2020203924A1 PCT/JP2020/014381 JP2020014381W WO2020203924A1 WO 2020203924 A1 WO2020203924 A1 WO 2020203924A1 JP 2020014381 W JP2020014381 W JP 2020014381W WO 2020203924 A1 WO2020203924 A1 WO 2020203924A1
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WIPO (PCT)
Prior art keywords
group
resin composition
epoxy resin
magnetic
mass
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PCT/JP2020/014381
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French (fr)
Japanese (ja)
Inventor
一郎 大浦
正応 依田
達也 本間
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味の素株式会社
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Priority to JP2021512086A priority Critical patent/JP7464044B2/en
Publication of WO2020203924A1 publication Critical patent/WO2020203924A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/32—Epoxy compounds containing three or more epoxy groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3442—Heterocyclic compounds having nitrogen in the ring having two nitrogen atoms in the ring
    • C08K5/3445—Five-membered rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/541—Silicon-containing compounds containing oxygen
    • C08K5/5435—Silicon-containing compounds containing oxygen containing oxygen in a ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F17/00—Fixed inductances of the signal type 
    • H01F17/04—Fixed inductances of the signal type  with magnetic core
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F27/00—Details of transformers or inductances, in general
    • H01F27/24—Magnetic cores
    • H01F27/255—Magnetic cores made from particles
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/16—Printed circuits incorporating printed electric components, e.g. printed resistor, capacitor, inductor

Definitions

  • the present invention relates to a resin composition containing a magnetic powder; a magnetic sheet containing the resin composition; a magnetically cured product of the resin composition; and an inductor substrate containing the magnetically cured product.
  • inductor substrates are mounted on information terminals such as mobile phones and smartphones.
  • independent inductor components were mounted on a substrate such as a circuit board, but in recent years, inductor substrates have been manufactured by a method in which a coil is formed by the conductor pattern of the substrate and the inductor is directly provided on the substrate. ing. Further, in recent years, further miniaturization of information terminals has been required, and an inductor having a high inductance has been required for miniaturization of inductance.
  • Patent Document 1 a method of directly providing an inductor on a substrate, for example, a method of screen-printing a resin composition containing a magnetic material on a substrate including wiring to form a magnetic layer is known (Patent Document 1, Patent Document). 2).
  • a magnetic layer for example, it is conceivable to form a magnetic layer by a cured product of a resin composition containing a magnetic powder and an epoxy resin, but a decrease in insulating property becomes an issue.
  • a decrease in insulating property becomes an issue.
  • it is effective to increase the content of the magnetic powder in the resin composition but as the content of the magnetic powder increases, the more This issue becomes apparent.
  • the present invention has been made in view of the above circumstances, and an object of the present invention is to provide a resin composition capable of suppressing a decrease in insulating property in a cured product of a resin composition containing a magnetic powder and an epoxy resin. And.
  • the present inventor has added (C) a siloxane compound having an alicyclic epoxy group to a resin composition containing (A) magnetic powder and (B) epoxy resin.
  • the component (C) is the formula (1):
  • R independently represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a substituted or unsubstituted aryl group, and X is independently substituted or unsubstituted, respectively.
  • the content of the component (A) is 60% by mass to 98% by mass when the non-volatile component in the resin composition is 100% by mass, according to any one of the above [1] to [3].
  • Resin composition. [5] The resin composition according to any one of the above [1] to [4], wherein the component (B) contains an epoxy resin liquid at 25 ° C.
  • the resin composition according to any one of the above [1] to [7] which is in the form of a paste at 25 ° C.
  • Magnetic cured product 130 ° C. of the resin composition, the resistance value of the magnetic cured product was allowed to stand for 200 hours at a relative humidity of 85% RH is at 1.0 ⁇ 10 6 ⁇ or more, the [1 ] To [8].
  • a magnetic sheet comprising a support and a resin composition layer provided on the support and formed of the resin composition according to any one of the above [1] to [10].
  • FIG. 1 is a schematic plan view of an inductor substrate according to an embodiment of the present invention.
  • the resin composition of the present invention contains (A) a magnetic powder, (B) an epoxy resin, and (C) a siloxane compound having an alicyclic epoxy group.
  • the magnetic powder Since the magnetic powder has a much lower resistance value than the epoxy resin, the coexistence of the magnetic powder and the epoxy resin having significantly different resistance values in the resin composition causes an electric charge at the interface between the magnetic powder and the epoxy resin. Is localized and insulation destruction is likely to occur, and it is considered that the insulation property is lowered.
  • the resin composition of the present invention contains (A) a magnetic powder, (B) an epoxy resin, and (C) a siloxane compound having an alicyclic epoxy group, (A) a magnetic powder. It is presumed that the interfacial charge between (B) and the epoxy resin can be delocalized and (A) the resistance value on the surface of the magnetic powder can be improved.
  • the magnetically cured product of the resin composition of the present invention has excellent insulating properties. In addition, such insulation is excellent in moisture resistance in one embodiment. Further, the magnetically cured product of the resin composition of the present invention has an excellent specific magnetic permeability in one embodiment.
  • the resin composition of the present invention may further contain any component in addition to (A) magnetic powder, (B) epoxy resin, and (C) a siloxane compound having an alicyclic epoxy group.
  • Optional components include, for example, (D) hardener, (E) and other additives.
  • the resin composition contains (A) magnetic powder.
  • Magnetic powder means a powdery magnetic material, and includes soft magnetic powder and hard magnetic powder.
  • the magnetic powder include pure iron powder; Mg—Zn-based ferrite powder, Fe—Mn-based ferrite powder, Fe—Zn-based ferrite powder, Mn—Zn-based ferrite powder, and Mn—Mg-based ferrite powder.
  • the magnetic powder (A) preferably contains one or more kinds selected from iron oxide powder and iron alloy-based metal powder, and more preferably iron oxide powder or iron alloy-based metal powder.
  • the iron oxide powder is preferably a ferrite powder containing at least one selected from Ni, Cu, Mn, Zn, Mg, Sr, Ba, and Co in addition to Fe, and is preferably Ni, Cu, Mn, and More preferably, it is a ferrite powder containing at least one selected from Zn.
  • the iron alloy-based metal powder may be an iron alloy-based metal powder containing at least one selected from Si, Cr, Al, Ni, Co, Mo, Mn, Zn, and Cu in addition to Fe. It is more preferable that the iron alloy-based metal powder contains at least one selected from Si, Cr, Al, Ni, Mn, Zn, and Co.
  • the magnetic powder (A) a commercially available magnetic powder can be used.
  • Specific examples of commercially available magnetic powders that can be used include “M05S” and “MZ05S” manufactured by Powder Tech Co., Ltd .; “PST-S” manufactured by Sanyo Special Steel Co., Ltd .; “PF-3F” and “AW2” manufactured by Epson Atmix Co., Ltd.
  • the magnetic powder may be used alone or in combination of two or more.
  • the magnetic powder is preferably spherical.
  • the value (aspect ratio) obtained by dividing the length of the major axis of the magnetic powder by the length of the minor axis is preferably 2 or less, more preferably 1.5 or less, still more preferably 1.2 or less.
  • the average particle size of the magnetic powder (A) is preferably 0.01 ⁇ m or more, more preferably 0.5 ⁇ m or more, still more preferably 1 ⁇ m or more, from the viewpoint of improving the specific magnetic permeability. Further, it is preferably 10 ⁇ m or less, more preferably 9 ⁇ m or less, and further preferably 8 ⁇ m or less.
  • the median diameter (D 50 ) of the magnetic powder (A) is preferably 0.01 ⁇ m or more, more preferably 0.5 ⁇ m or more, still more preferably 1 ⁇ m or more, from the viewpoint of improving the relative magnetic permeability. Further, it is preferably 10 ⁇ m or less, more preferably 9 ⁇ m or less, and further preferably 8 ⁇ m or less.
  • the average particle size of the magnetic powder can be measured by a laser diffraction / scattering method based on the Mie scattering theory. Specifically, it can be measured by creating a particle size distribution of magnetic powder on a volume basis with a laser diffraction / scattering type particle size distribution measuring device and using the median diameter as the average particle size. As the measurement sample, a magnetic powder dispersed in water by ultrasonic waves can be preferably used. As the laser diffraction / scattering type particle size distribution measuring device, "LA-960" manufactured by HORIBA, Ltd., "SALD-2200” manufactured by Shimadzu Corporation, or the like can be used.
  • the specific surface area of the magnetic powder can be measured by the BET method.
  • the content (% by volume) of the magnetic powder (A) is preferably 10% by volume when the non-volatile component in the resin composition is 100% by volume from the viewpoint of improving the relative magnetic permeability and reducing the loss coefficient. As mentioned above, it is more preferably 20% by volume or more, still more preferably 30% by volume or more. Further, it is preferably 85% by volume or less, more preferably 80% by volume or less, and further preferably 75% by volume or less.
  • the content (mass%) of the magnetic powder (A) is preferably 60% by mass when the non-volatile component in the resin composition is 100% by mass from the viewpoint of improving the relative magnetic permeability and reducing the loss coefficient. As mentioned above, it is more preferably 70% by mass or more, and further preferably 75% by mass or more. Further, it is preferably 98% by mass or less, more preferably 95% by mass or less, and further preferably 90% by mass or less.
  • the resin composition of the present invention contains (B) an epoxy resin.
  • the (B) epoxy resin is a resin having an epoxy group and means a resin composed of a skeleton atom selected from a carbon atom, an oxygen atom and a nitrogen atom, and a silicon atom is used as a skeleton atom as in the component (C). Contains resin is not included.
  • Examples of the (B) epoxy resin include bixilenol type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, dicyclopentadiene type epoxy resin, and trisphenol type.
  • One type of epoxy resin may be used alone, or two or more types may be used in combination.
  • the resin composition preferably contains an epoxy resin having two or more epoxy groups in one molecule as the (B) epoxy resin.
  • the ratio of the epoxy resin having two or more epoxy groups in one molecule is preferably 50% by mass with respect to 100% by mass of the non-volatile component of the epoxy resin (B). % Or more, more preferably 60% by mass or more, and particularly preferably 70% by mass or more.
  • the epoxy resin may be a liquid epoxy resin at a temperature of 25 ° C. (hereinafter sometimes referred to as “liquid epoxy resin”) or a solid epoxy resin at a temperature of 25 ° C. (hereinafter referred to as “solid epoxy resin”). ).
  • the resin composition of the present invention comprises a liquid epoxy resin as the epoxy resin.
  • the resin composition of the present invention comprises a solid epoxy resin as the epoxy resin.
  • the resin composition of the present invention may contain only the liquid epoxy resin or only the solid epoxy resin as the epoxy resin, and may contain a combination of the liquid epoxy resin and the solid epoxy resin. However, in a preferred embodiment, only the liquid epoxy resin is included.
  • liquid epoxy resin a liquid epoxy resin having two or more epoxy groups in one molecule is preferable.
  • liquid epoxy resin examples include glycyrrole type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, glycidylamine type epoxy resin, and phenol novolac type epoxy.
  • a resin, an alicyclic epoxy resin having an ester skeleton, a cyclohexane type epoxy resin, a cyclohexanedimethanol type epoxy resin, and an epoxy resin having a butadiene structure are preferable, and a glycylol type epoxy resin, a bisphenol A type epoxy resin, and a bisphenol F type epoxy are preferable.
  • Resin is more preferred.
  • liquid epoxy resin examples include “HP4032”, “HP4032D”, and “HP4032SS” (naphthalene type epoxy resin) manufactured by DIC; “828US”, “828EL”, “jER828EL”, and “825" manufactured by Mitsubishi Chemical Co., Ltd.
  • JP-100 epoxy resin having a butadiene structure
  • ZX1658 liquid 1,4-glycidylcyclohexane type epoxy resin
  • Nippon Steel & Sumitomo Metal Chemical Co., Ltd. and the like can be mentioned. These may be used individually by 1 type, and may be used in combination of 2 or more types.
  • solid epoxy resin a solid epoxy resin having 3 or more epoxy groups in one molecule is preferable, and an aromatic solid epoxy resin having 3 or more epoxy groups in one molecule is more preferable.
  • solid epoxy resin examples include bixilenol type epoxy resin, naphthalene type epoxy resin, naphthalene type tetrafunctional epoxy resin, cresol novolac type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, naphthol type epoxy resin, and biphenyl.
  • Type epoxy resin, naphthylene ether type epoxy resin, anthracene type epoxy resin, bisphenol A type epoxy resin, bisphenol AF type epoxy resin, and tetraphenylethane type epoxy resin are preferable.
  • solid epoxy resin examples include "HP4032H” (naphthalene type epoxy resin) manufactured by DIC; “HP-4700” and “HP-4710” (naphthalene type tetrafunctional epoxy resin) manufactured by DIC; DIC.
  • the mass ratio of the liquid epoxy resin to the solid epoxy resin is preferably 1 or more. It is preferably 10 or more, and particularly preferably 50 or more.
  • the epoxy equivalent of the (B) epoxy resin is preferably 50 g / eq. ⁇ 5000g / eq. , More preferably 50 g / eq. ⁇ 3000g / eq. , More preferably 80 g / eq. ⁇ 2000g / eq. , Even more preferably 110 g / eq. ⁇ 1000g / eq. Is. Within this range, the crosslink density of the magnetically cured product of the magnetic sheet becomes sufficient, and an insulating layer having a small surface roughness can be provided.
  • Epoxy equivalent is the mass of a resin containing 1 equivalent of an epoxy group. This epoxy equivalent can be measured according to JIS K7236.
  • the weight average molecular weight (Mw) of the epoxy resin is preferably 100 to 5000, more preferably 250 to 3000, and further preferably 400 to 1500 from the viewpoint of remarkably obtaining the desired effect of the present invention.
  • the weight average molecular weight of the resin can be measured as a polystyrene-equivalent value by a gel permeation chromatography (GPC) method.
  • the content of the epoxy resin (B) is not particularly limited, but is preferably 1 when the non-volatile component in the resin composition is 100% by mass from the viewpoint of remarkably obtaining the desired effect of the present invention. It is by mass% or more, more preferably 5% by mass or more, still more preferably 8% by mass or more, and particularly preferably 10% by mass or more.
  • the upper limit is preferably 40% by mass or less, more preferably 30% by mass or less, still more preferably 25% by mass or less, and particularly preferably 20% by mass or less, from the viewpoint of remarkably obtaining the desired effect of the present invention.
  • the resin composition of the present invention contains (C) a siloxane compound having an alicyclic epoxy group.
  • the siloxane compound refers to a compound having a siloxane (Si—O—Si) bond.
  • the siloxane compound in the present invention may be a cyclic siloxane or a chain siloxane.
  • the siloxane compound in the present invention has preferably 10 or less, more preferably 5 or less, and particularly preferably 4 or less silicon atoms forming a siloxane bond. It is preferable that all the substitutable sites of the silicon atom in the siloxane compound are substituted with a hydrocarbon group such as an alkyl group, an alkenyl group, or an aryl group having or not having an alicyclic epoxy group.
  • the hydrocarbon group may have a substituent other than the alicyclic epoxy group.
  • the alicyclic epoxy group a saturated or an aliphatic carbon ring group unsaturated, -CH 2 -CH 2 in the aliphatic carbon ring - two hydrogen atoms bonded to a portion different carbon atoms of 1 A group that is substituted with an oxygen atom to form an oxacyclopropane ring.
  • the alicyclic epoxy group include a 2,3-epoxycyclopentyl group, a 3,4-epoxycyclopentyl group, a 2,3-epoxycyclohexyl group, and a 3,4-epoxycyclohexyl group having 4 to 10 carbon atoms.
  • Epoxycycloalkyl groups and the like can be mentioned.
  • the siloxane compound in the present invention preferably has two or more alicyclic epoxy groups, preferably 10 or less, more preferably 5 or less, and particularly preferably 4 or less.
  • the component (C) is preferably the formula (1):
  • R independently represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a substituted or unsubstituted aryl group, and X is independently substituted or unsubstituted, respectively.
  • R independently represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a substituted or unsubstituted aryl group, preferably a substituted or unsubstituted alkyl. It is a group, more preferably a (unsubstituted) alkyl group, and particularly preferably a methyl group or an ethyl group.
  • X independently represents a substituted or unsubstituted alkylene group, preferably a (unsubstituted) alkylene group, and particularly preferably -CH 2- or -CH 2- CH 2- .
  • Y represents an alicyclic epoxy group independently of each other, and is preferably an epoxycycloalkyl group having 4 to 10 carbon atoms, and particularly preferably a 3,4-epoxycyclohexyl group.
  • n represents an integer of 1 or more, preferably an integer of 1 to 9, more preferably an integer of 1 to 4, and particularly preferably an integer of 1 to 3.
  • R 1 and R 2 independently represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a substituted or unsubstituted aryl group, or preferably a substituted or unsubstituted alkyl group.
  • n is preferably 2 or more.
  • alkyl group refers to a linear, branched or cyclic monovalent aliphatic saturated hydrocarbon group.
  • the "alkyl group” is preferably an alkyl group having 1 to 6 carbon atoms, and more preferably an alkyl group having 1 to 3 carbon atoms.
  • Examples of the “alkyl group” include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, cyclopentyl group and cyclohexyl. Examples thereof include a methyl group and an ethyl group.
  • alkenyl group refers to a linear, branched or cyclic monovalent aliphatic unsaturated hydrocarbon group having at least one carbon-carbon double bond.
  • the "alkenyl group” is preferably an alkenyl group having 2 to 6 carbon atoms, and more preferably an alkenyl group having 2 or 3 carbon atoms.
  • Examples of the “alkenyl group” include vinyl group, 1-propenyl group, 2-propenyl group, 2-methyl-1-propenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group and 3-methyl-.
  • alkylene group refers to a linear, branched or cyclic divalent aliphatic saturated hydrocarbon group.
  • the "alkylene group” is preferably an alkylene group having 1 to 6 carbon atoms, and more preferably an alkylene group having 1 to 3 carbon atoms.
  • alkylene group for example, -CH 2 -, - CH 2 -CH 2 -, - CH (CH 3) -, - CH 2 -CH 2 -CH 2 -, - CH 2 -CH (CH 3) -, - CH (CH 3) -CH 2 -, - C (CH 3) 2 -, - CH 2 -CH 2 -CH 2 -CH 2 -, - CH 2 -CH 2 -CH (CH 3) -, -CH 2 -CH (CH 3) -CH 2 -, - CH (CH 3) -CH 2 -CH 2 -, - CH (CH 3) -CH 2 -CH 2 -, - CH 2 -C (CH 3) 2 -, - C (CH 3) 2 -CH 2 -Etc., preferably -CH 2- or -CH 2- CH 2- .
  • the alkyl group in the "substituted or unsubstituted alkyl group", the alkenyl group in the “substituted or unsubstituted alkenyl group”, and the substituent of the alkylene group in the "substituted or unsubstituted alkylene group” are particularly limited. Although not, for example, a halogen atom, a cyano group, an alkoxy group, an alkylcarbonyl group, an aryl group, a heteroaryl group, an aryloxy group, an arylcarbonyl group, an amino group, a nitro group, a hydroxy group, etc., or a group obtained by combining these. Can be mentioned.
  • the number of substituents is preferably 1 to 3, and more preferably 1.
  • Aryl group refers to a monovalent aromatic hydrocarbon group.
  • the "aryl group” is preferably an aryl group having 6 to 14 carbon atoms, and more preferably an aryl group having 6 to 10 carbon atoms.
  • Examples of the “aryl group” include a phenyl group, a 1-naphthyl group, a 2-naphthyl group and the like, and a phenyl group is preferable.
  • the substituent of the aryl group in the "substituted or unsubstituted aryl group” is not particularly limited, but for example, a halogen atom, a cyano group, an alkyl group, an alkoxy group, an alkylcarbonyl group, an aryl group, or a heteroaryl. Examples thereof include a group, an aryloxy group, an arylcarbonyl group, an aralkyl group, an amino group, a nitro group, a hydroxy group and the like, or a group in which these are combined.
  • the number of substituents is preferably 1 to 3, and more preferably 1.
  • halogen atom examples include a fluorine atom, a chlorine atom, a bromine atom and the like.
  • alkoxy group refers to a monovalent group (alkyl-O-) formed by bonding an alkyl group to an oxygen atom.
  • the "alkoxy group” is preferably an alkoxy group having 1 to 6 carbon atoms, and more preferably an alkoxy group having 1 to 3 carbon atoms.
  • alkoxy group examples include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group, a sec-butoxy group, a tert-butoxy group, a pentyloxy group and the like.
  • alkylcarbonyl group refers to a monovalent group (alkyl-CO-) formed by bonding an alkyl group to a carbonyl.
  • the "alkylcarbonyl group” is preferably an alkylcarbonyl group having 2 to 7 carbon atoms, and more preferably an alkylcarbonyl group having 2 to 4 carbon atoms.
  • alkylcarbonyl group examples include an acetyl group, a propanoyl group, a butanoyl group, a 2-methylpropanol group, a pentanoyl group, a 3-methylbutanoyl group, a 2-methylbutanoyl group, and a 2,2-dimethylpropanoyl.
  • Examples include a group, a hexanoyl group, a heptanoyle group and the like.
  • heteroaryl group refers to a monovalent aromatic heterocyclic group having 1 to 4 heteroatoms selected from an oxygen atom, a nitrogen atom and a sulfur atom in addition to a carbon atom as a ring-constituting atom.
  • the "heteroaryl group” is preferably a 5- to 12-membered (preferably 5- or 6-membered) monocyclic, bicyclic or tricyclic (preferably monocyclic) aromatic heterocyclic group.
  • heteroaryl group examples include a frill group, a thienyl group, a pyrrolyl group, an oxazolyl group, an isooxazolyl group, a thiazolyl group, an isothiazolyl group, an imidazolyl group, a pyrazolyl group, 1,2,3-oxadiazolyl group, 1,2, 4-Oxaziazolyl group, 1,3,4-oxadiazolyl group, Frazanyl group, 1,2,3-thiadiazolyl group, 1,2,4-thiadiazolyl group, 1,3,4-thiadiazolyl group, 1,2,3- Examples thereof include a triazolyl group, a 1,2,4-triazolyl group, a tetrazolyl group, a pyridyl group, a pyridadinyl group, a pyrimidinyl group, a pyrazinyl group and a triazinyl group.
  • aryloxy group refers to a monovalent group (aryl-O-) formed by bonding an aryl group to an oxygen atom.
  • the "aryloxy group” is preferably an aryloxy group having 6 to 14 carbon atoms, and more preferably an aryloxy group having 6 to 10 carbon atoms. Examples of the “aryloxy group” include a phenoxy group and a naphthoxy group.
  • the “arylcarbonyl group” refers to a monovalent group (aryl-CO-) formed by bonding an aryl group to a carbonyl.
  • the "arylcarbonyl group” is preferably an arylcarbonyl group having 7 to 15 carbon atoms, and more preferably an arylcarbonyl group having 7 to 11 carbon atoms.
  • Examples of the “arylcarbonyl group” include a benzoyl group, a 1-naphthoyl group, a 2-naphthoyl group and the like.
  • the “aralkyl group” refers to an alkyl group substituted with one or more aryl groups.
  • the “aralkyl group” is preferably an aralkyl group having 7 to 15 carbon atoms, and more preferably an aralkyl group having 7 to 11 carbon atoms. Examples of the “aralkyl group” include a benzyl group, a phenethyl group, a 2-naphthylmethyl group and the like.
  • the molecular weight of the component (C) is preferably 2,000 or less, more preferably 1,500 or less, still more preferably 1,000 or less, and particularly preferably 800 or less.
  • the lower limit may be, for example, 200 or more.
  • the epoxy equivalent of the component (C) is preferably 50 g / eq. ⁇ 1000g / eq. , More preferably 100 g / eq. ⁇ 500 g / eq. , More preferably 150 g / eq. ⁇ 300 g / eq. , Particularly preferably 150 g / eq. ⁇ 250 g / eq. Is.
  • component (C) As a specific example of the component (C), "KR-470” manufactured by Shin-Etsu Chemical Co., Ltd. (main component: 2,4,6,8-tetraxane (2- (3,4-epoxycyclohexane) ethyl) -2,4 , 6,8-Tetramethylcyclotetrasiloxane), "X-40-2667” (main component: 1,3,5-tris (2- (3,4-epoxycyclohexyl) ethyl) -1,1,3 5,5-Pentamethyltrisiloxane), "X-40-2715” (main component: 1,3-bis (2- (3,4-epoxycyclohexyl) ethyl) -1,1,3,3-tetramethyl Disiloxane) and the like. These may be used individually by 1 type, and may be used in combination of 2 or more types.
  • the content of the component (C) is not particularly limited, but from the viewpoint of remarkably obtaining the desired effect of the present invention, when the non-volatile component in the resin composition is 100% by mass, it is preferably 0. It is 1% by mass or more, more preferably 1% by mass or more, still more preferably 2% by mass or more, and particularly preferably 3% by mass or more.
  • the upper limit is preferably 50% by mass or less, more preferably 30% by mass or less, still more preferably 20% by mass or less, and particularly preferably 15% by mass or less, from the viewpoint of remarkably obtaining the desired effect of the present invention.
  • the resin composition of the present invention may contain (D) a curing agent as an optional component.
  • (D) a curing agent By containing (D) a curing agent, (B) the epoxy resin can be cured more easily.
  • the (D) curing agent includes (B) an epoxy resin curing agent having a function of curing the epoxy resin and (B) a curing accelerator having a function of accelerating the curing of the epoxy resin.
  • the curing agent preferably contains either an epoxy resin curing agent or a curing accelerator, and more preferably contains an epoxy resin curing agent.
  • the epoxy resin curing agent is not particularly limited as long as it has a function of curing the epoxy resin.
  • a phenol-based curing agent, a naphthol-based curing agent, an acid anhydride-based curing agent, an active ester-based curing agent, and a benzoxazine-based curing agent examples thereof include agents, cyanate ester-based curing agents, carbodiimide-based curing agents, and imidazole-based curing agents.
  • an acid anhydride-based curing agent and an imidazole-based curing agent are preferable, and an imidazole-based curing agent is particularly preferable.
  • the epoxy resin curing agent may be used alone or in combination of two or more.
  • a phenol-based curing agent having a novolak structure or a naphthol-based curing agent having a novolak structure is preferable from the viewpoint of heat resistance and water resistance. Further, from the viewpoint of adhesion to the adherend, a nitrogen-containing phenol-based curing agent or a nitrogen-containing naphthol-based curing agent is preferable, and a triazine skeleton-containing phenol-based curing agent or a triazine skeleton-containing naphthol-based curing agent is more preferable.
  • a triazine skeleton-containing phenol novolac resin is preferable from the viewpoint of highly satisfying heat resistance, water resistance, and adhesion.
  • the phenol-based curing agent and the naphthol-based curing agent include, for example, "MEH-7700”, “MEH-7810", “MEH-7851”, “MEH-8000H” manufactured by Meiwa Kasei Co., Ltd., and Nippon Kayaku Co., Ltd. "NHN”, “CBN”, “GPH” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.
  • the acid anhydride-based curing agent examples include a curing agent having one or more acid anhydride groups in one molecule.
  • Specific examples of the acid anhydride-based curing agent include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic acid anhydride, and methylnadic hydride.
  • the active ester-based curing agent is not particularly limited, but generally contains an ester group having high reactive activity such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds in one molecule.
  • a compound having two or more esters is preferably used.
  • the active ester-based curing agent is preferably obtained by a condensation reaction between a carboxylic acid compound and / or a thiocarboxylic acid compound and a hydroxy compound and / or a thiol compound.
  • an active ester-based curing agent obtained from a carboxylic acid compound and a hydroxy compound is preferable, and an active ester-based curing agent obtained from a carboxylic acid compound and a phenol compound and / or a naphthol compound is more preferable.
  • the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid and the like.
  • phenol compound or naphthol compound examples include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthaline, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-.
  • the "dicyclopentadiene-type diphenol compound” refers to a diphenol compound obtained by condensing two phenol molecules with one dicyclopentadiene molecule.
  • an active ester compound containing a dicyclopentadiene-type diphenol structure an active ester compound containing a naphthalene structure, an active ester compound containing an acetylated product of phenol novolac, and an active ester compound containing a benzoylated product of phenol novolac are preferable.
  • an active ester compound containing a naphthalene structure and an active ester compound containing a dicyclopentadiene-type diphenol structure are more preferable.
  • the "dicyclopentadiene-type diphenol structure” represents a divalent structural unit composed of phenylene-dicyclopentalene-phenylene.
  • benzoxazine-based curing agent examples include "JBZ-OP100D” and “ODA-BOZ” manufactured by JFE Chemical Co., Ltd .; “HFB2006M” manufactured by Showa High Polymer Co., Ltd. and “Pd” manufactured by Shikoku Chemicals Corporation. Examples include “FA”.
  • cyanate ester-based curing agent examples include bisphenol A disicianate, polyphenol cyanate (oligo (3-methylene-1,5-phenylencyanate)), 4,4'-methylenebis (2,6-dimethylphenylcyanate), 4, 4'-Etilidendidiphenyl disianate, hexafluorobisphenol A disyanate, 2,2-bis (4-cyanate) phenylpropane, 1,1-bis (4-cyanate phenylmethane), bis (4-cyanate-3,5-) Bifunctional cyanate resins such as dimethylphenyl) methane, 1,3-bis (4-cyanatephenyl-1- (methylethylidene)) benzene, bis (4-cyanatephenyl) thioether, and bis (4-cyanatephenyl) ether, Examples thereof include polyfunctional cyanate resins derived from phenol novolac, cresol novolak and the like, and prepolymers in which these cyanate resin
  • cyanate ester-based curing agent examples include "PT30” and “PT60” (both are phenol novolac type polyfunctional cyanate ester resins), "BA230”, and “BA230S75” (part of bisphenol A disocyanate) manufactured by Lonza Japan.
  • PT30 and "PT60” (both are phenol novolac type polyfunctional cyanate ester resins), "BA230”, and “BA230S75” (part of bisphenol A disocyanate) manufactured by Lonza Japan.
  • a prepolymer in which all of them are triazined to form a trimer can be mentioned.
  • carbodiimide-based curing agent examples include “V-03” and “V-07” manufactured by Nisshinbo Chemical Co., Ltd.
  • imidazole-based curing agent examples include 2-methylimidazole, 2-undecyl imidazole, 2-heptadecyl imidazole, 1,2-dimethyl imidazole, 2-ethyl-4-methyl imidazole, 1,2-dimethyl imidazole, 2 -Ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1 -Cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimerite, 1-cyanoethyl-2 -Phenylimida
  • imidazole-based curing agent a commercially available product may be used, and examples thereof include "P200-H50” manufactured by Mitsubishi Chemical Corporation.
  • the amount ratio of the epoxy resin to the epoxy resin curing agent is the ratio of [total number of epoxy groups in the epoxy resin]: [total number of reactive groups in the epoxy resin curing agent], which is 1: 0.2 to 1: 2.
  • the range is preferable, 1: 0.3 to 1: 1.5 is more preferable, and 1: 0.4 to 1: 1.2 is even more preferable.
  • the reactive group of the epoxy resin curing agent is an active hydroxyl group, an active ester group, or the like, and differs depending on the type of the curing agent.
  • the total number of epoxy groups in the epoxy resin is the total number of all epoxy resins obtained by dividing the mass of non-volatile components of each epoxy resin by the epoxy equivalent, and is the total number of reactive groups in the epoxy resin curing agent.
  • the curing accelerator examples include amine-based curing accelerators, imidazole-based curing accelerators, phosphorus-based curing accelerators, guanidine-based curing accelerators, and metal-based curing accelerators.
  • an amine-based curing accelerator, an imidazole-based curing accelerator, and a guanidine-based curing accelerator are preferable, and an imidazole-based curing accelerator is more preferable.
  • the curing accelerator may be used alone or in combination of two or more.
  • the curing accelerator is generally used in combination with the curing agent.
  • amine-based curing accelerator examples include triethylamine, tributylamine, 4-dimethylaminopyridine (DMAP), benzyldimethylamine, 2,4,6, -tris (dimethylaminomethyl) phenol, and 1,8-diazabicyclo (5).
  • DMAP 4-dimethylaminopyridine
  • benzyldimethylamine 2,4,6, -tris (dimethylaminomethyl) phenol
  • 1,8-diazabicyclo (5) examples include triethylamine, tributylamine, 4-dimethylaminopyridine (DMAP), benzyldimethylamine, 2,4,6, -tris (dimethylaminomethyl) phenol, and 1,8-diazabicyclo (5).
  • imidazole-based curing accelerator examples include those described in the above-mentioned imidazole-based curing agent. When used in combination with other curing agents, the imidazole-based curing agent may function as a curing accelerator.
  • imidazole-based curing accelerator a commercially available product may be used, and examples thereof include those described in the above-mentioned imidazole-based curing agent.
  • Examples of the phosphorus-based curing accelerator include triphenylphosphine, phosphonium borate compound, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, and (4-methylphenyl) triphenylphosphonium thiocyanate. , Tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate and the like.
  • guanidine-based curing accelerator examples include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1- (o-tolyl) guanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, and the like.
  • the metal-based curing accelerator examples include organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin.
  • organic metal complex examples include an organic cobalt complex such as cobalt (II) acetylacetonate and cobalt (III) acetylacetonate, an organic copper complex such as copper (II) acetylacetonate, and zinc (II) acetylacetonate.
  • organic zinc complexes such as iron (III) acetylacetonate, organic nickel complexes such as nickel (II) acetylacetonate, and organic manganese complexes such as manganese (II) acetylacetonate.
  • organic metal salt include zinc octylate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, zinc stearate and the like.
  • the content of the curing agent (D) is not particularly limited, but when the non-volatile component in the resin composition is 100% by mass, it is preferably 25% by mass or less, more preferably 15% by mass or less, and further. It is preferably 10% by mass or less.
  • the lower limit is not particularly limited, and may be, for example, 0.01% by mass or more, 0.1% by mass or more, 0.5% by mass or more, 1% by mass or more, and the like.
  • the resin composition may further contain (E) and other additives, if necessary.
  • Such other additives include, for example, other resin components, silane coupling agents, non-magnetic inorganic fillers, dispersants, curing retardants, flame retardants, thickeners, defoamers, leveling agents, adhesions. Examples thereof include additives, resin additives such as colorants, and organic solvents. The content of other additives can be appropriately set by those skilled in the art.
  • the resin composition of the present invention contains (C) a siloxane compound having an alicyclic epoxy group to delocalize the interfacial charges between (A) the magnetic powder and (B) the epoxy resin.
  • the resistance value of the magnetically cured product obtained by thermosetting the resin composition of the present invention after being left at 130 ° C. and a relative humidity of 85% RH for 200 hours is preferably 1.
  • ⁇ 10 6 ⁇ or more more preferably 1.0 ⁇ 10 7 ⁇ or more, still more preferably 1.0 ⁇ 10 8 ⁇ or more, even more preferably 1.0 ⁇ 10 9 ⁇ or more, particularly preferably 1.0.
  • ⁇ 10 Can be 10 ⁇ or more.
  • the magnetically cured product of the resin composition of the present invention has an excellent specific magnetic permeability in one embodiment.
  • the specific magnetic permeability ( ⁇ ') of the magnetically cured product obtained by thermosetting the resin composition of the present invention at 23 ° C. is preferably 6.0 or more, more preferably 7.0 or more, and even more preferably 7.0 or more. It can be 8.0 or higher, particularly preferably 8.5 or higher.
  • the resin composition can be produced, for example, by a method of stirring the compounding components using a stirring device such as a three-roll, rotary mixer, or high-speed rotary mixer.
  • the resin composition may be defoamed after production or the like. Examples thereof include defoaming by standing, defoaming by centrifugation, vacuum defoaming, stirring defoaming, and defoaming by a combination thereof.
  • the resin composition may be used in the form of a paste-like resin composition (magnetic paste) at room temperature (25 ° C.), and the magnetic sheet containing the layer of the resin composition may be used. It may be used in a form.
  • the resin composition can be a paste-like magnetic paste even if it does not contain an organic solvent.
  • the content thereof is preferably less than 1.0% by mass, more preferably 0.8% by mass or less, still more preferably 0.5% by mass, based on the total mass of the magnetic paste.
  • it is particularly preferably 0.1% by mass or less.
  • the lower limit is 0.001% by mass or more, or no content, without particular limitation.
  • the viscosity of the magnetic paste is preferably 20 Pa ⁇ s or more, more preferably 25 Pa ⁇ s or more, further preferably 30 Pa ⁇ s or more, 50 Pa ⁇ s or more at 25 ° C., and usually less than 200 Pa ⁇ s, preferably 180 Pa ⁇ s. Hereinafter, it is more preferably 160 Pa ⁇ s or less.
  • the viscosity can be measured using an E-type viscometer while keeping the temperature of the magnetic paste at 25 ⁇ 2 ° C.
  • the resin composition of the present invention can be thermally cured by heating to obtain a magnetically cured product.
  • thermosetting conditions for obtaining a magnetically cured product differ depending on the composition and type of the resin composition, but the thermosetting temperature is preferably 120 ° C. or higher, more preferably 130 ° C. or higher, still more preferably 150 ° C. or higher. It is preferably 240 ° C. or lower, more preferably 220 ° C. or lower, and even more preferably 200 ° C. or lower.
  • the thermosetting time for obtaining the magnetically cured product is preferably 5 minutes or more, more preferably 10 minutes or more, still more preferably 15 minutes or more, preferably 120 minutes or less, more preferably 100 minutes or less, still more preferably. 90 minutes or less.
  • the resin composition Before the resin composition is thermosetting, the resin composition may be subjected to a preheat treatment in which the resin composition is heated at a temperature lower than the curing temperature.
  • the temperature of the preheat treatment is preferably 50 ° C. or higher, preferably 60 ° C. or higher, more preferably 70 ° C. or higher, preferably less than 120 ° C., preferably 110 ° C. or lower, and more preferably 100 ° C. or higher.
  • the time of the preheat treatment is usually preferably 5 minutes or more, more preferably 15 minutes or more, preferably 150 minutes or less, and more preferably 120 minutes or less.
  • the magnetic sheet includes a support and a resin composition layer formed of the resin composition provided on the support.
  • the thickness of the resin composition layer is preferably 250 ⁇ m or less, more preferably 200 ⁇ m or less, still more preferably 150 ⁇ m or less, 100 ⁇ m or less from the viewpoint of thinning.
  • the lower limit of the thickness of the resin composition layer is not particularly limited, but may be usually 5 ⁇ m or more.
  • Examples of the support include a film made of a plastic material, a metal foil, and a paper pattern, and a film made of a plastic material and a metal foil are preferable.
  • the plastic material may be, for example, polyethylene terephthalate (hereinafter abbreviated as "PET”) or polyethylene naphthalate (hereinafter abbreviated as “PEN”).
  • PET polyethylene terephthalate
  • PEN polyethylene naphthalate
  • PC polycarbonate
  • acrylics such as polymethylmethacrylate (PMMA)
  • PMMA polymethylmethacrylate
  • TAC triacetylcellulose
  • PES polyethersulfide
  • ketones include ketones and polyethylene.
  • polyethylene terephthalate and polyethylene naphthalate are preferable, and inexpensive polyethylene terephthalate is particularly preferable.
  • the metal foil When a metal foil is used as the support, examples of the metal foil include copper foil and aluminum foil, and copper foil is preferable.
  • the copper foil a foil made of a single metal of copper may be used, and a foil made of an alloy of copper and another metal (for example, tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) may be used. You may use it.
  • the support may be matted or corona-treated on the surface to be joined to the resin composition layer.
  • a support with a release layer having a release layer on the surface to be joined with the resin composition layer may be used.
  • the release agent used for the release layer of the support with the release layer include one or more release agents selected from the group consisting of alkyd resin, polyolefin resin, urethane resin, and silicone resin. ..
  • a commercially available product may be used.
  • “SK-1” and “SK-1” manufactured by Lintec Corporation which are PET films having a release layer containing an alkyd resin-based release agent as a main component. Examples include “AL-5" and “AL-7", “Lumirror T60” manufactured by Toray Industries, Inc., “Purex” manufactured by Teijin Corporation, and "Unipee” manufactured by Unitika.
  • the thickness of the support is not particularly limited, but is preferably in the range of 5 ⁇ m to 75 ⁇ m, and more preferably in the range of 10 ⁇ m to 60 ⁇ m.
  • the thickness of the entire support with a release layer is preferably in the above range.
  • a magnetic paste in which a resin composition is dissolved in an organic solvent is prepared, and this magnetic paste is applied onto a support using a die coater or the like, and further dried to form a resin composition layer. It can be manufactured by.
  • the resin composition is in the form of a paste, it can be produced by directly applying the resin composition onto the support using a die coater or the like to form a resin composition layer.
  • organic solvent examples include ketones such as acetone, methyl ethyl ketone (MEK) and cyclohexanone, acetic acid esters such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate and carbitol acetate, cellosolve and butyl carbitol and the like.
  • ketones such as acetone, methyl ethyl ketone (MEK) and cyclohexanone
  • acetic acid esters such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate and carbitol acetate, cellosolve and butyl carbitol and the like.
  • carbitols aromatic hydrocarbons such as toluene and xylene
  • amide solvents such as dimethylformamide, dimethylacetamide (DMAc) and
  • Drying may be carried out by a known method such as heating or blowing hot air.
  • the drying conditions are not particularly limited, but the resin composition layer is dried so that the content of the organic solvent is 10% by mass or less, preferably 5% by mass or less. Although it depends on the boiling point of the organic solvent in the magnetic paste, for example, when a magnetic paste containing 30% by mass to 60% by mass of an organic solvent is used, the resin composition is obtained by drying at 50 ° C. to 150 ° C. for 3 to 10 minutes. A material layer can be formed.
  • a protective film similar to the support can be further laminated on the surface of the resin composition layer that is not bonded to the support (that is, the surface opposite to the support).
  • the thickness of the protective film is not particularly limited, but is, for example, 1 ⁇ m to 40 ⁇ m.
  • the inductor substrate of the present invention contains a magnetic layer which is a cured product of the resin composition (magnetic paste or the like) of the present invention.
  • a coil is formed by the conductor pattern of the substrate, and not only the inductor substrate on which the inductor is provided on the substrate but also the substrate provided with the inductor is mounted on the substrate such as a circuit board as a component such as a chip inductor.
  • the inductor substrate is also included.
  • FIG. 1 is a schematic plan view of an inductor substrate according to an embodiment of the present invention.
  • the inductor substrate 1 includes a substrate 11, a magnetic layer 12, and a wiring 13 formed of a conductor.
  • the wiring 13 is covered with the magnetic layer 12, and the wiring 13 is formed in a spiral shape around the core portion 14. Has been done. Further, a magnetic layer 12 is embedded in the core portion 14.
  • the manufacturing method of the inductor substrate is (1) A step of discharging a resin composition onto a substrate, thermosetting the resin composition, and forming a first magnetic layer. (2) Step of forming wiring on the first magnetic layer, (3) A step of ejecting a resin composition onto a first magnetic layer, a core portion and wiring, and thermosetting the resin composition to form a second magnetic layer. including.
  • the magnetic layer 12 includes the first and second magnetic layers.
  • the resin composition is discharged onto the substrate and the resin composition is thermosetting to form the first magnetic layer.
  • a step of preparing the resin composition may be included.
  • the substrate is usually an insulating substrate.
  • the substrate material include insulating substrates such as glass epoxy substrates, metal substrates, polyester substrates, polyimide substrates, BT resin substrates, and thermosetting polyphenylene ether substrates.
  • the substrate may be an inner layer circuit board in which wiring or the like is built within the thickness thereof.
  • the resin composition is filled in a syringe, a needle, a cartridge, or the like, and is applied onto the substrate by discharging the resin composition with a discharge device such as a dispenser. Further, the resin composition may be applied onto the substrate by full-face printing or pattern printing. After coating, it is thermoset to obtain a first magnetic layer.
  • the thermosetting conditions of the resin composition differ depending on the composition and type of the resin composition, but the curing temperature is preferably 120 ° C. or higher, more preferably 130 ° C. or higher, still more preferably 150 ° C. or higher, preferably 240 ° C. or higher. Below, it is more preferably 220 ° C. or lower, still more preferably 200 ° C. or lower.
  • the curing time of the resin composition is preferably 5 minutes or more, more preferably 10 minutes or more, further preferably 15 minutes or more, preferably 120 minutes or less, more preferably 100 minutes or less, still more preferably 90 minutes or less. is there.
  • the resin composition Before the resin composition is thermosetting, the resin composition may be subjected to a preheat treatment in which the resin composition is heated at a temperature lower than the curing temperature.
  • the temperature of the preheat treatment is preferably 50 ° C. or higher, preferably 60 ° C. or higher, more preferably 70 ° C. or higher, preferably less than 120 ° C., preferably 110 ° C. or lower, and more preferably 100 ° C. or higher.
  • the time of the preheat treatment is usually preferably 5 minutes or more, more preferably 15 minutes or more, preferably 150 minutes or less, and more preferably 120 minutes or less.
  • the wiring is formed on the first magnetic layer formed in the step (1).
  • the wiring forming method include a plating method, a sputtering method, a vapor deposition method, and the like, and the plating method is particularly preferable.
  • the surface of the first magnetic layer is plated by an appropriate method such as a semi-additive method or a full-additive method to form a wiring having a spiral wiring pattern.
  • Wiring materials include, for example, single metals such as gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin and indium; gold, platinum, palladium, silver, Examples include alloys of two or more metals selected from the group of copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin and indium. Above all, from the viewpoint of versatility, cost, ease of patterning, etc., it is possible to use chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or nickel-chromium alloy, copper nickel alloy, copper titanium alloy. It is preferable to use chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or a nickel-chromium alloy, and it is even more preferable to use copper.
  • single metals such as gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium
  • a plating seed layer is formed on the surface of the first magnetic layer by electroless plating.
  • an electrolytic plating layer is formed on the formed plating seed layer by electrolytic plating, and if necessary, an unnecessary plating seed layer is removed by a treatment such as etching to form a wiring having a desired wiring pattern. it can.
  • annealing treatment may be performed if necessary for the purpose of improving the peel strength of the wiring. The annealing treatment can be performed, for example, by heating the substrate at 150 to 200 ° C. for 20 to 90 minutes.
  • a mask pattern is formed on the formed plating seed layer to expose a part of the plating seed layer corresponding to the spiral pattern.
  • the mask pattern is removed after forming an electrolytic plating layer by electrolytic plating on the exposed plating seed layer. Then, the unnecessary plating seed layer is removed by a treatment such as etching to form a wiring having a desired pattern.
  • the thickness of the wiring is preferably 70 ⁇ m or less, more preferably 60 ⁇ m or less, still more preferably 50 ⁇ m or less, still more preferably 40 ⁇ m or less, particularly preferably 30 ⁇ m or less, 20 ⁇ m or less, 15 ⁇ m from the viewpoint of thinning. It is less than or equal to 10 ⁇ m or less.
  • the lower limit is preferably 1 ⁇ m or more, more preferably 3 ⁇ m or more, still more preferably 5 ⁇ m or more.
  • the resin composition is discharged onto the first magnetic layer, the core portion and the wiring, and the resin composition is thermosetting to form the second magnetic layer.
  • the method for forming the second magnetic layer is the same as that for the first magnetic layer.
  • the resin composition forming the first magnetic layer and the resin composition forming the second magnetic layer may be the same or different from each other.
  • a step of forming an insulating layer on the first magnetic layer may be provided. Further, after the step (2), a step of forming an insulating layer on the wiring may be provided.
  • the insulating layer may be formed in the same manner as the insulating layer of the circuit board, or the same material as the insulating layer of the circuit board may be used.
  • the circuit board includes the inductor board of the present invention.
  • the circuit board can be used as a board for mounting electronic components such as semiconductor chips, and can also be used as a multi-layer circuit board (multi-layer printed wiring board) using such a circuit board as an inner layer board. Further, the circuit board can be used as an individualized chip inductor component, or the chip inductor component can be used as a surface-mounted circuit board.
  • various types of semiconductor devices can be manufactured by using such a circuit board.
  • the semiconductor device including such a circuit board can be suitably used for electric products (for example, computers, mobile phones, digital cameras, televisions, etc.) and vehicles (for example, motorcycles, automobiles, trains, ships, aircraft, etc.) and the like. ..
  • Example 1 80 parts by mass of magnetic powder (“M05S” manufactured by Powder Tech, Fe-Mn-based ferrite powder, D 50 (median diameter): 5 ⁇ m) with respect to 80 parts by mass of a siloxane compound (“KR-470”, main component: the following formula 5 parts by mass of the compound (2), manufactured by Shin-Etsu Chemical Co., Ltd., 8 parts of bisphenol type epoxy resin ("ZX-1059", a mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin, manufactured by Nippon Steel & Sumitomo Metal Corporation)
  • ZX-1059 bisphenol type epoxy resin
  • EP-3980S glycidyl ether type nitrogen-containing aromatic epoxy, manufactured by ADEKA
  • imidazole-based curing agent 2P4MZ
  • 2-phenyl-4-methylimidazole 2 parts by mass (manufactured by Shikoku Kasei Co., Ltd.) was added and uniformly dispersed with a
  • Example 2 Instead of 5 parts by mass of siloxane compound ("KR-470", manufactured by Shin-Etsu Chemical Co., Ltd.), 5 parts by mass of siloxane compound ("X-40-2667", main component: compound of the following formula (3), manufactured by Shin-Etsu Chemical Co., Ltd.) A resin composition was prepared in the same manner as in Example 1 except that the parts were used.
  • Example 3 Instead of 5 parts by mass of siloxane compound ("KR-470", manufactured by Shin-Etsu Chemical Co., Ltd.), 5 parts by mass of siloxane compound ("X-40-2715", main component: compound of the following formula (4), manufactured by Shin-Etsu Chemical Co., Ltd.) A resin composition was prepared in the same manner as in Example 1 except that the parts were used.
  • Example 4 Magnetic powder (Powder Tech “M05S”, Fe-Mn-based ferrite powder, D 50 (median diameter): 5 ⁇ m) Instead of 80 parts by mass, magnetic powder (Powder Tech “MZ05S”, Fe-Zn) A resin composition was prepared in the same manner as in Example 1 except that 80 parts by mass of the system ferrite powder, D 50 (median diameter): 5 ⁇ m) was used.
  • Magnetic powder (“M05S” manufactured by Powder Tech, Fe-Mn-based ferrite powder, D 50 (median diameter): 5 ⁇ m) Instead of 80 parts by mass, magnetic powder (“PF-3F” manufactured by Epson Atmix), Fe-Si-based alloy powder, D 50 (median diameter): 3 [mu] m) were used in place of the 80 parts by weight, in the same manner as in example 1 to prepare a resin composition.
  • ⁇ Test Example 1 Measurement of relative magnetic permeability>
  • a polyethylene terephthalate (PET) film (“PET501010” manufactured by Lintec Corporation, thickness 50 ⁇ m) treated with a silicone-based release agent was prepared.
  • PET501010 polyethylene terephthalate
  • Each of the resin compositions of Examples and Comparative Examples was uniformly applied on the release surface of the PET film with a doctor blade so that the thickness of the paste layer after drying was 100 ⁇ m to obtain a magnetic sheet.
  • the obtained magnetic sheet was heated at 180 ° C. for 90 minutes to thermally cure the paste layer, and the support was peeled off to obtain a sheet-like magnetically cured product.
  • the obtained magnetically cured product was cut into test pieces having a width of 5 mm and a length of 18 mm to prepare an evaluation sample.
  • This evaluation sample was measured using Agilent Technologies (manufactured by Agilent Technologies, "HP8362B") at a measurement frequency of 100 MHz by a 3-turn coil method and a specific magnetic permeability ( ⁇ ') at room temperature (23 ° C.). ..
  • ⁇ Test Example 2 Insulation test>
  • the resin compositions of Examples and Comparative Examples were uniformly applied onto the TAB tape with a doctor blade so that the thickness of the paste layer after drying was 100 ⁇ m, and samples were obtained.
  • the resin composition was thermoset by heating the obtained sample at 180 ° C. for 90 minutes to obtain a cured sample.
  • the HAST tester (“ETAC PM422” manufactured by Kusumoto Kasei Co., Ltd.) was left at 130 ° C. and a relative humidity of 85% RH for 200 hours, and then the resistance value (HAST resistance value) ( ⁇ ) was measured. did.
  • Table 1 below shows the non-volatile components of the resin compositions of Examples and Comparative Examples, their contents, and the measurement results of Test Examples.

Abstract

The present invention provides a resin composition that makes it possible to improve the insulation of magnetic cured products. The present invention is a resin composition that includes (A) a magnetic powder, (B) an epoxy resin, and (C) a siloxane compound that has an alicyclic epoxy group.

Description

磁性粉体を含む樹脂組成物Resin composition containing magnetic powder
　本発明は、磁性粉体を含む樹脂組成物；当該樹脂組成物を含む磁性シート；当該樹脂組成物の磁性硬化物；及び当該磁性硬化物を含むインダクタ基板に関する。 The present invention relates to a resin composition containing a magnetic powder; a magnetic sheet containing the resin composition; a magnetically cured product of the resin composition; and an inductor substrate containing the magnetically cured product.
　インダクタを有する基板（インダクタ基板）は、携帯電話機、スマートフォンなどの情報端末に数多く搭載されている。従来は独立したインダクタ部品が回路基板等の基板に実装されていたが、近年は基板の導体パターンによりコイルを形成し、インダクタを基板に直接設ける手法によりインダクタ基板の製造が行われるようになってきている。また、近年、情報端末のさらなる小型化が求められており、インダクタンスの小型化のために、高いインダクタンスを有するインダクタが必要とされるようになってきている。 Many substrates with inductors (inductor substrates) are mounted on information terminals such as mobile phones and smartphones. In the past, independent inductor components were mounted on a substrate such as a circuit board, but in recent years, inductor substrates have been manufactured by a method in which a coil is formed by the conductor pattern of the substrate and the inductor is directly provided on the substrate. ing. Further, in recent years, further miniaturization of information terminals has been required, and an inductor having a high inductance has been required for miniaturization of inductance.
　インダクタを基板に直接設ける手法としては、例えば、磁性材料を含有する樹脂組成物を、配線を含む基板上にスクリーン印刷して磁性層を形成する方法が知られている（特許文献１、特許文献２参照）。 As a method of directly providing an inductor on a substrate, for example, a method of screen-printing a resin composition containing a magnetic material on a substrate including wiring to form a magnetic layer is known (Patent Document 1, Patent Document). 2).
特開平６－６９０５８号公報JP-A-6-69058 特開２０１７－６３１００号公報JP-A-2017-63100
　このような磁性層としては、例えば、磁性粉体とエポキシ樹脂を含む樹脂組成物の硬化物により磁性層を形成することが考えられるが、絶縁性の低下が課題となる。特に、高インダクタンス達成のため、磁性層の比透磁率を高める場合、樹脂組成物中の磁性粉体の含有量を高くすることが有効であるが、磁性粉体の含有量が増大するほど、この課題が顕在化する。 As such a magnetic layer, for example, it is conceivable to form a magnetic layer by a cured product of a resin composition containing a magnetic powder and an epoxy resin, but a decrease in insulating property becomes an issue. In particular, when increasing the relative magnetic permeability of the magnetic layer in order to achieve high inductance, it is effective to increase the content of the magnetic powder in the resin composition, but as the content of the magnetic powder increases, the more This issue becomes apparent.
　本発明は、上記の事情に鑑みてなされたものであり、磁性粉体とエポキシ樹脂を含む樹脂組成物の硬化物において、絶縁性の低下を抑制しうる、樹脂組成物を提供することを目的とする。 The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a resin composition capable of suppressing a decrease in insulating property in a cured product of a resin composition containing a magnetic powder and an epoxy resin. And.
　本発明者は、上記目的を達成すべく鋭意研究をした結果、（Ａ）磁性粉体と（Ｂ）エポキシ樹脂を含む樹脂組成物に、（Ｃ）脂環式エポキシ基を有するシロキサン化合物を配合することにより、樹脂組成物の磁性硬化物の絶縁性を向上させることができることを見出し、本発明を完成するに至った。 As a result of diligent research to achieve the above object, the present inventor has added (C) a siloxane compound having an alicyclic epoxy group to a resin composition containing (A) magnetic powder and (B) epoxy resin. By doing so, it has been found that the insulating property of the magnetically cured product of the resin composition can be improved, and the present invention has been completed.
　すなわち、本発明は以下の内容を含む。
［１］　（Ａ）磁性粉体、（Ｂ）エポキシ樹脂、及び（Ｃ）脂環式エポキシ基を有するシロキサン化合物を含む樹脂組成物。
［２］　（Ｃ）成分が、式（１）： That is, the present invention includes the following contents.
[1] A resin composition containing (A) a magnetic powder, (B) an epoxy resin, and (C) a siloxane compound having an alicyclic epoxy group.
[2] The component (C) is the formula (1):
Figure JPOXMLDOC01-appb-C000002
Figure JPOXMLDOC01-appb-C000002
〔式中、Ｒは、それぞれ独立して、置換又は無置換のアルキル基、置換又は無置換のアルケニル基、又は置換又は無置換のアリール基を示し、Ｘは、それぞれ独立して、置換又は無置換のアルキレン基を示し、Ｙは、それぞれ独立して、脂環式エポキシ基を示し、ｎは、１以上の整数を示し、Ｒ１及びＲ２は、それぞれ独立して、置換又は無置換のアルキル基、置換又は無置換のアルケニル基、又は置換又は無置換のアリール基を示すか、或いはＲ１及びＲ２が一緒になって１個の－Ｏ－を示して互いに結合し、環状シロキサンを形成する。〕
で表される化合物である、上記［１］に記載の樹脂組成物。
［３］　（Ａ）成分が、酸化鉄粉及び鉄合金系金属粉からなる群より選ばれる１種類以上を含む、上記［１］又は［２］に記載の樹脂組成物。
［４］　（Ａ）成分の含有量が、樹脂組成物中の不揮発成分を１００質量％とした場合、６０質量％～９８質量％である、上記［１］～［３］の何れかに記載の樹脂組成物。
［５］　（Ｂ）成分が、２５℃で液状のエポキシ樹脂を含む、上記［１］～［４］の何れかに記載の樹脂組成物。
［６］　さらに（Ｄ）硬化剤を含む、上記［１］～［５］の何れかに記載の樹脂組成物。
［７］　（Ｄ）成分が、イミダゾール系硬化剤である、上記［６］に記載の樹脂組成物。
［８］　２５℃でペースト状である、上記［１］～［７］の何れかに記載の樹脂組成物。
［９］　樹脂組成物の磁性硬化物を１３０℃、相対湿度８５％ＲＨにて２００時間放置した後の当該磁性硬化物の抵抗値が、１．０×１０６Ω以上である、上記［１］～［８］の何れかに記載の樹脂組成物。
［１０］　樹脂組成物の磁性硬化物の２３℃での比透磁率（μ’）が、６．０以上である、上記［１］～［９］の何れかに記載の樹脂組成物。
［１１］　支持体と、当該支持体上に設けられた上記［１］～［１０］の何れかに記載の樹脂組成物で形成された樹脂組成物層とを含む、磁性シート。
［１２］　上記［１］～［１０］の何れかに記載の樹脂組成物の磁性硬化物。
［１３］　上記［１２］に記載の磁性硬化物を含むインダクタ基板。 [In the formula, R independently represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a substituted or unsubstituted aryl group, and X is independently substituted or unsubstituted, respectively. Substituted alkylene groups, Y each independently represents an alicyclic epoxy group, n represents an integer greater than or equal to 1, and R 1 and R 2 are independently substituted or unsubstituted, respectively. An alkyl group, a substituted or unsubstituted alkenyl group, or a substituted or unsubstituted aryl group is shown, or R 1 and R 2 are combined to show one —O— and bonded to each other to form a cyclic siloxane. Form. ]
The resin composition according to the above [1], which is a compound represented by.
[3] The resin composition according to the above [1] or [2], wherein the component (A) contains at least one selected from the group consisting of iron oxide powder and iron alloy-based metal powder.
[4] The content of the component (A) is 60% by mass to 98% by mass when the non-volatile component in the resin composition is 100% by mass, according to any one of the above [1] to [3]. Resin composition.
[5] The resin composition according to any one of the above [1] to [4], wherein the component (B) contains an epoxy resin liquid at 25 ° C.
[6] The resin composition according to any one of the above [1] to [5], which further contains (D) a curing agent.
[7] The resin composition according to the above [6], wherein the component (D) is an imidazole-based curing agent.
[8] The resin composition according to any one of the above [1] to [7], which is in the form of a paste at 25 ° C.
[9] Magnetic cured product 130 ° C. of the resin composition, the resistance value of the magnetic cured product was allowed to stand for 200 hours at a relative humidity of 85% RH is at 1.0 × 10 6 Ω or more, the [1 ] To [8].
[10] The resin composition according to any one of the above [1] to [9], wherein the magnetically cured product of the resin composition has a specific magnetic permeability (μ') at 23 ° C. of 6.0 or more.
[11] A magnetic sheet comprising a support and a resin composition layer provided on the support and formed of the resin composition according to any one of the above [1] to [10].
[12] The magnetically cured product of the resin composition according to any one of the above [1] to [10].
[13] An inductor substrate containing the magnetically cured product according to the above [12].
　本発明の樹脂組成物によれば、優れた絶縁性を有する磁性硬化物を得ることができる。 According to the resin composition of the present invention, a magnetically cured product having excellent insulating properties can be obtained.
図１は、本発明の一実施形態に係るインダクタ基板の模式的な平面図である。FIG. 1 is a schematic plan view of an inductor substrate according to an embodiment of the present invention.
　以下、本発明をその好適な実施形態に即して詳細に説明する。ただし、本発明は、下記実施形態及び例示物に限定されるものではなく、本発明の請求の範囲及びその均等の範囲を逸脱しない範囲において任意に変更して実施され得る。 Hereinafter, the present invention will be described in detail according to its preferred embodiment. However, the present invention is not limited to the following embodiments and examples, and may be arbitrarily modified and implemented without departing from the scope of claims of the present invention and the equivalent scope thereof.
［樹脂組成物］
　本発明の樹脂組成物は、（Ａ）磁性粉体、（Ｂ）エポキシ樹脂、及び（Ｃ）脂環式エポキシ基を有するシロキサン化合物を含む。 [Resin composition]
The resin composition of the present invention contains (A) a magnetic powder, (B) an epoxy resin, and (C) a siloxane compound having an alicyclic epoxy group.
　磁性粉体はエポキシ樹脂と比べて抵抗値が非常に低いため、樹脂組成物中に抵抗値が大きく異なる磁性粉とエポキシ樹脂とが共存することにより、磁性粉とエポキシ樹脂との界面にて電荷が局在化し絶縁破壊が起こりやすく、絶縁性が低下すると考えられる。本発明の樹脂組成物は、（Ａ）磁性粉体、及び（Ｂ）エポキシ樹脂に加えて、（Ｃ）脂環式エポキシ基を有するシロキサン化合物が配合されているため、（Ａ）磁性粉体と（Ｂ）エポキシ樹脂との界面電荷を非局在化させ、（Ａ）磁性粉体表面の抵抗値を向上させることができると推測される。このように、本発明の樹脂組成物の磁性硬化物は、優れた絶縁性を有する。また、このような絶縁性は、一実施形態において、耐湿性に優れる。また、本発明の樹脂組成物の磁性硬化物は、一実施形態において、優れた比透磁率を有する。 Since the magnetic powder has a much lower resistance value than the epoxy resin, the coexistence of the magnetic powder and the epoxy resin having significantly different resistance values in the resin composition causes an electric charge at the interface between the magnetic powder and the epoxy resin. Is localized and insulation destruction is likely to occur, and it is considered that the insulation property is lowered. Since the resin composition of the present invention contains (A) a magnetic powder, (B) an epoxy resin, and (C) a siloxane compound having an alicyclic epoxy group, (A) a magnetic powder. It is presumed that the interfacial charge between (B) and the epoxy resin can be delocalized and (A) the resistance value on the surface of the magnetic powder can be improved. As described above, the magnetically cured product of the resin composition of the present invention has excellent insulating properties. In addition, such insulation is excellent in moisture resistance in one embodiment. Further, the magnetically cured product of the resin composition of the present invention has an excellent specific magnetic permeability in one embodiment.
　本発明の樹脂組成物は、（Ａ）磁性粉体、（Ｂ）エポキシ樹脂、及び（Ｃ）脂環式エポキシ基を有するシロキサン化合物の他に、さらに任意の成分を含んでいてもよい。任意の成分としては、例えば、（Ｄ）硬化剤、（Ｅ）その他の添加剤が挙げられる。以下、樹脂組成物に含まれる各成分について詳細に説明する。 The resin composition of the present invention may further contain any component in addition to (A) magnetic powder, (B) epoxy resin, and (C) a siloxane compound having an alicyclic epoxy group. Optional components include, for example, (D) hardener, (E) and other additives. Hereinafter, each component contained in the resin composition will be described in detail.
＜（Ａ）磁性粉体＞
　樹脂組成物は、（Ａ）磁性粉体を含有する。 <(A) Magnetic powder>
The resin composition contains (A) magnetic powder.
　（Ａ）磁性粉体とは、粉末状の磁性体を意味し、軟磁性粉体、及び硬磁性粉体が含まれる。（Ａ）磁性粉体としては、例えば、純鉄粉末；Ｍｇ－Ｚｎ系フェライト粉末、Ｆｅ－Ｍｎ系フェライト粉末、Ｆｅ－Ｚｎ系フェライト粉末、Ｍｎ－Ｚｎ系フェライト粉末、Ｍｎ－Ｍｇ系フェライト粉末、Ｃｕ－Ｚｎ系フェライト粉末、Ｍｇ－Ｍｎ－Ｓｒ系フェライト粉末、Ｎｉ－Ｚｎ系フェライト粉末、Ｂａ－Ｚｎ系フェライト粉末、Ｂａ－Ｍｇ系フェライト粉末、Ｂａ－Ｎｉ系フェライト粉末、Ｂａ－Ｃｏ系フェライト粉末、Ｂａ－Ｎｉ－Ｃｏ系フェライト粉末、Ｙ系フェライト粉末、酸化鉄粉（ＩＩＩ）、四酸化三鉄などの酸化鉄粉；Ｆｅ－Ｓｉ系合金粉末、Ｆｅ－Ｓｉ－Ａｌ系合金粉末、Ｆｅ－Ｃｒ系合金粉末、Ｆｅ－Ｃｒ－Ｓｉ系合金粉末、Ｆｅ－Ｎｉ－Ｃｒ系合金粉末、Ｆｅ－Ｃｒ－Ａｌ系合金粉末、Ｆｅ－Ｎｉ系合金粉末、Ｆｅ－Ｎｉ－Ｍｏ系合金粉末、Ｆｅ－Ｎｉ－Ｍｏ－Ｃｕ系合金粉末、Ｆｅ－Ｃｏ系合金粉末、Ｆｅ－Ｍｎ系合金粉末、Ｆｅ－Ｚｎ系合金粉末、あるいはＦｅ－Ｎｉ－Ｃｏ系合金粉末などの鉄合金系金属粉；Ｃｏ基アモルファスなどのアモルファス合金粉等が挙げられる。 (A) Magnetic powder means a powdery magnetic material, and includes soft magnetic powder and hard magnetic powder. Examples of the magnetic powder include pure iron powder; Mg—Zn-based ferrite powder, Fe—Mn-based ferrite powder, Fe—Zn-based ferrite powder, Mn—Zn-based ferrite powder, and Mn—Mg-based ferrite powder. Cu-Zn-based ferrite powder, Mg-Mn-Sr-based ferrite powder, Ni-Zn-based ferrite powder, Ba-Zn-based ferrite powder, Ba-Mg-based ferrite powder, Ba-Ni-based ferrite powder, Ba-Co-based ferrite powder , Ba—Ni—Co-based ferrite powder, Y-based ferrite powder, iron oxide powder (III), iron oxide powder such as triiron tetroxide; Fe—Si based alloy powder, Fe—Si—Al alloy powder, Fe- Cr-based alloy powder, Fe-Cr-Si-based alloy powder, Fe-Ni-Cr-based alloy powder, Fe-Cr-Al-based alloy powder, Fe-Ni-based alloy powder, Fe-Ni-Mo-based alloy powder, Fe- Iron alloy-based metal powder such as Ni—Mo—Cu alloy powder, Fe—Co alloy powder, Fe—Mn alloy powder, Fe—Zn alloy powder, or Fe—Ni—Co alloy powder; Co-based amorphous Such as amorphous alloy powder and the like.
　中でも、（Ａ）磁性粉体としては、酸化鉄粉及び鉄合金系金属粉から選ばれる１種類以上を含むことが好ましく、酸化鉄粉又は鉄合金系金属粉であることがより好ましい。酸化鉄粉としては、Ｆｅに加えて、Ｎｉ、Ｃｕ、Ｍｎ、Ｚｎ、Ｍｇ、Ｓｒ、Ｂａ、及びＣｏから選ばれる少なくとも１種を含むフェライト粉末であることが好ましく、Ｎｉ、Ｃｕ、Ｍｎ、及びＺｎから選ばれる少なくとも１種を含むフェライト粉末であることがより好ましい。また、鉄合金系金属粉としては、Ｆｅに加えて、Ｓｉ、Ｃｒ、Ａｌ、Ｎｉ、Ｃｏ、Ｍｏ、Ｍｎ、Ｚｎ、及びＣｕから選ばれる少なくとも１種を含む鉄合金系金属粉であることが好ましく、Ｓｉ、Ｃｒ、Ａｌ、Ｎｉ、Ｍｎ、Ｚｎ、及びＣｏから選ばれる少なくとも１種を含む鉄合金系金属粉であることがより好ましい。 Among them, the magnetic powder (A) preferably contains one or more kinds selected from iron oxide powder and iron alloy-based metal powder, and more preferably iron oxide powder or iron alloy-based metal powder. The iron oxide powder is preferably a ferrite powder containing at least one selected from Ni, Cu, Mn, Zn, Mg, Sr, Ba, and Co in addition to Fe, and is preferably Ni, Cu, Mn, and More preferably, it is a ferrite powder containing at least one selected from Zn. The iron alloy-based metal powder may be an iron alloy-based metal powder containing at least one selected from Si, Cr, Al, Ni, Co, Mo, Mn, Zn, and Cu in addition to Fe. It is more preferable that the iron alloy-based metal powder contains at least one selected from Si, Cr, Al, Ni, Mn, Zn, and Co.
　（Ａ）磁性粉体としては、市販の磁性粉体を用いることができる。用いられ得る市販の磁性粉体の具体例としては、パウダーテック社製「Ｍ０５Ｓ」、「ＭＺ０５Ｓ」；山陽特殊製鋼社製「ＰＳＴ－Ｓ」；エプソンアトミックス社製「ＰＦ－３Ｆ」、「ＡＷ２－０８」、「ＡＷ２－０８ＰＦ２０Ｆ」、「ＡＷ２－０８ＰＦ１０Ｆ」、「ＡＷ２－０８ＰＦ３Ｆ」、「Ｆｅ－３．５Ｓｉ－４．５ＣｒＰＦ２０Ｆ」、「Ｆｅ－５０ＮｉＰＦ２０Ｆ」、「Ｆｅ－８０Ｎｉ－４ＭｏＰＦ２０Ｆ」；ＪＦＥケミカル社製「ＬＤ－Ｍ」、「ＬＤ－ＭＨ」、「ＫＮＩ－１０６」、「ＫＮＩ－１０６ＧＳＭ」、「ＫＮＩ－１０６ＧＳ」、「ＫＮＩ－１０９」、「ＫＮＩ－１０９ＧＳＭ」、「ＫＮＩ－１０９ＧＳ」；戸田工業社製「ＫＮＳ－４１５」、「ＢＳＦ－５４７」、「ＢＳＦ－０２９」、「ＢＳＮ－１２５」、「ＢＳＮ－１２５」、「ＢＳＮ－７１４」、「ＢＳＮ－８２８」、「Ｓ－１２８１」、「Ｓ－１６４１」、「Ｓ－１６５１」、「Ｓ－１４７０」、「Ｓ－１５１１」、「Ｓ－２４３０」；日本重化学工業社製「ＪＲ０９Ｐ２」；ＣＩＫナノテック社製「Ｎａｎｏｔｅｋ」；キンセイマテック社製「ＪＥＭＫ－Ｓ」、「ＪＥＭＫ－Ｈ」；ＡＬＤＲＩＣＨ社製「Ｙｔｔｒｉｕｍ　ｉｒｏｎ　ｏｘｉｄｅ」等が挙げられる。磁性粉体は１種単独で用いてもよく、又は２種以上を併用してもよい。 As the magnetic powder (A), a commercially available magnetic powder can be used. Specific examples of commercially available magnetic powders that can be used include "M05S" and "MZ05S" manufactured by Powder Tech Co., Ltd .; "PST-S" manufactured by Sanyo Special Steel Co., Ltd .; "PF-3F" and "AW2" manufactured by Epson Atmix Co., Ltd. -08 "," AW2-08PF20F "," AW2-08PF10F "," AW2-08PF3F "," Fe-3.5Si-4.5CrPF20F "," Fe-50NiPF20F "," Fe-80Ni-4MoPF20F "; JFE Chemical "LD-M", "LD-MH", "KNI-106", "KNI-106GSM", "KNI-106GS", "KNI-109", "KNI-109GSM", "KNI-109GS"; "KNS-415", "BSF-547", "BSF-029", "BSN-125", "BSN-125", "BSN-714", "BSN-828", "S-1281" manufactured by Toda Kogyo Co., Ltd. , "S-1641", "S-1651", "S-1470", "S-1511", "S-2430"; "JR09P2" manufactured by Nippon Heavy Chemical Industries, Ltd .; "Nanotek" manufactured by CIK Nanotech Co., Ltd .; Kinsei "JEMK-S" and "JEMK-H" manufactured by Matek Co., Ltd .; "Ytrium iron oxide" manufactured by ALDRICH and the like can be mentioned. The magnetic powder may be used alone or in combination of two or more.
　（Ａ）磁性粉体は、球状であることが好ましい。磁性粉体の長軸の長さを短軸の長さで除した値（アスペクト比）としては、好ましくは２以下、より好ましくは１．５以下、さらに好ましくは１．２以下である。一般に、磁性粉体は球状ではない扁平な形状であるほうが、比透磁率を向上させやすい。しかし、特に球状の磁性粉体を用いる方が、通常、磁気損失を低くでき、またペースト状の樹脂組成物を得たい場合、好ましい粘度を有するペーストを得る観点から好ましい。 (A) The magnetic powder is preferably spherical. The value (aspect ratio) obtained by dividing the length of the major axis of the magnetic powder by the length of the minor axis is preferably 2 or less, more preferably 1.5 or less, still more preferably 1.2 or less. In general, it is easier to improve the relative magnetic permeability when the magnetic powder has a flat shape that is not spherical. However, it is usually preferable to use a spherical magnetic powder from the viewpoint of obtaining a paste having a preferable viscosity when it is possible to reduce the magnetic loss and obtain a paste-like resin composition.
　（Ａ）磁性粉体の平均粒径は、比透磁率を向上させる観点から、好ましくは０．０１μｍ以上、より好ましくは０．５μｍ以上、さらに好ましくは１μｍ以上である。また、好ましくは１０μｍ以下、より好ましくは９μｍ以下、さらに好ましくは８μｍ以下である。（Ａ）磁性粉体のメジアン径（Ｄ５０）は、比透磁率を向上させる観点から、好ましくは０．０１μｍ以上、より好ましくは０．５μｍ以上、さらに好ましくは１μｍ以上である。また、好ましくは１０μｍ以下、より好ましくは９μｍ以下、さらに好ましくは８μｍ以下である。 The average particle size of the magnetic powder (A) is preferably 0.01 μm or more, more preferably 0.5 μm or more, still more preferably 1 μm or more, from the viewpoint of improving the specific magnetic permeability. Further, it is preferably 10 μm or less, more preferably 9 μm or less, and further preferably 8 μm or less. The median diameter (D 50 ) of the magnetic powder (A) is preferably 0.01 μm or more, more preferably 0.5 μm or more, still more preferably 1 μm or more, from the viewpoint of improving the relative magnetic permeability. Further, it is preferably 10 μm or less, more preferably 9 μm or less, and further preferably 8 μm or less.
　（Ａ）磁性粉体の平均粒径はミー（Ｍｉｅ）散乱理論に基づくレーザー回折・散乱法により測定することができる。具体的にはレーザー回折散乱式粒径分布測定装置により、磁性粉体の粒径分布を体積基準で作成し、そのメディアン径を平均粒径とすることで測定することができる。測定サンプルは、磁性粉体を超音波により水中に分散させたものを好ましく使用することができる。レーザー回折散乱式粒径分布測定装置としては、堀場製作所社製「ＬＡ－９６０」、島津製作所社製「ＳＡＬＤ－２２００」等を使用することができる。 (A) The average particle size of the magnetic powder can be measured by a laser diffraction / scattering method based on the Mie scattering theory. Specifically, it can be measured by creating a particle size distribution of magnetic powder on a volume basis with a laser diffraction / scattering type particle size distribution measuring device and using the median diameter as the average particle size. As the measurement sample, a magnetic powder dispersed in water by ultrasonic waves can be preferably used. As the laser diffraction / scattering type particle size distribution measuring device, "LA-960" manufactured by HORIBA, Ltd., "SALD-2200" manufactured by Shimadzu Corporation, or the like can be used.
　（Ａ）磁性粉体の比表面積は、比透磁率を向上させる観点から、好ましくは０．０５ｍ２／ｇ以上、より好ましくは０．１ｍ２／ｇ以上、さらに好ましくは０．３ｍ２／ｇ以上である。また、好ましくは１０ｍ２／ｇ以下、より好ましくは８ｍ２／ｇ以下、さらに好ましくは５ｍ２／ｇ以下である。（Ａ）磁性粉体の比表面積は、ＢＥＴ法によって測定できる。 (A) a specific surface area of the magnetic powder, from the viewpoint of improving the relative permeability, preferably 0.05 m 2 / g or more, more preferably 0.1 m 2 / g or more, more preferably 0.3 m 2 / g That is all. Further, it is preferably 10 m 2 / g or less, more preferably 8 m 2 / g or less, and further preferably 5 m 2 / g or less. (A) The specific surface area of the magnetic powder can be measured by the BET method.
　（Ａ）磁性粉体の含有量（体積％）は、比透磁率を向上させ及び損失係数を低減させる観点から、樹脂組成物中の不揮発成分を１００体積％とした場合、好ましくは１０体積％以上、より好ましくは２０体積％以上、さらに好ましくは３０体積％以上である。また、好ましくは８５体積％以下、より好ましくは８０体積％以下、さらに好ましくは７５体積％以下である。 The content (% by volume) of the magnetic powder (A) is preferably 10% by volume when the non-volatile component in the resin composition is 100% by volume from the viewpoint of improving the relative magnetic permeability and reducing the loss coefficient. As mentioned above, it is more preferably 20% by volume or more, still more preferably 30% by volume or more. Further, it is preferably 85% by volume or less, more preferably 80% by volume or less, and further preferably 75% by volume or less.
　（Ａ）磁性粉体の含有量（質量％）は、比透磁率を向上させ及び損失係数を低減させる観点から、樹脂組成物中の不揮発成分を１００質量％とした場合、好ましくは６０質量％以上、より好ましくは７０質量％以上、さらに好ましくは７５質量％以上である。また、好ましくは９８質量％以下、より好ましくは９５質量％以下、さらに好ましくは９０質量％以下である。 The content (mass%) of the magnetic powder (A) is preferably 60% by mass when the non-volatile component in the resin composition is 100% by mass from the viewpoint of improving the relative magnetic permeability and reducing the loss coefficient. As mentioned above, it is more preferably 70% by mass or more, and further preferably 75% by mass or more. Further, it is preferably 98% by mass or less, more preferably 95% by mass or less, and further preferably 90% by mass or less.
＜（Ｂ）エポキシ樹脂＞
　本発明の樹脂組成物は、（Ｂ）エポキシ樹脂を含有する。（Ｂ）エポキシ樹脂とは、エポキシ基を有する樹脂であって、炭素原子、酸素原子及び窒素原子から選ばれる骨格原子からなる樹脂を意味し、（Ｃ）成分のように骨格原子としてケイ素原子を含む樹脂は含まれない。 <(B) Epoxy resin>
The resin composition of the present invention contains (B) an epoxy resin. The (B) epoxy resin is a resin having an epoxy group and means a resin composed of a skeleton atom selected from a carbon atom, an oxygen atom and a nitrogen atom, and a silicon atom is used as a skeleton atom as in the component (C). Contains resin is not included.
　（Ｂ）エポキシ樹脂としては、例えば、ビキシレノール型エポキシ樹脂、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、ビスフェノールＡＦ型エポキシ樹脂、ジシクロペンタジエン型エポキシ樹脂、トリスフェノール型エポキシ樹脂、ナフトールノボラック型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、ｔｅｒｔ－ブチル－カテコール型エポキシ樹脂、ナフタレン型エポキシ樹脂、ナフトール型エポキシ樹脂、アントラセン型エポキシ樹脂、グリシジルアミン型エポキシ樹脂、グリシジルエステル型エポキシ樹脂、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、線状脂肪族エポキシ樹脂、ブタジエン構造を有するエポキシ樹脂、脂環式エポキシ樹脂、複素環式エポキシ樹脂、スピロ環含有エポキシ樹脂、シクロヘキサン型エポキシ樹脂、シクロヘキサンジメタノール型エポキシ樹脂、ナフチレンエーテル型エポキシ樹脂、トリメチロール型エポキシ樹脂、テトラフェニルエタン型エポキシ樹脂等が挙げられる。エポキシ樹脂は、１種類単独で用いてもよく、２種類以上を組み合わせて用いてもよい。 Examples of the (B) epoxy resin include bixilenol type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, dicyclopentadiene type epoxy resin, and trisphenol type. Epoxy resin, naphthol novolac type epoxy resin, phenol novolac type epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, glycidylamine type epoxy resin, glycidyl ester type epoxy resin , Cresol novolac type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, epoxy resin having butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring-containing epoxy resin, cyclohexane type epoxy resin, cyclohexane Examples thereof include a dimethanol type epoxy resin, a naphthylene ether type epoxy resin, a trimethylol type epoxy resin, and a tetraphenylethane type epoxy resin. One type of epoxy resin may be used alone, or two or more types may be used in combination.
　樹脂組成物は、（Ｂ）エポキシ樹脂として、１分子中に２個以上のエポキシ基を有するエポキシ樹脂を含むことが好ましい。本発明の所望の効果を顕著に得る観点から、（Ｂ）エポキシ樹脂の不揮発成分１００質量％に対して、１分子中に２個以上のエポキシ基を有するエポキシ樹脂の割合は、好ましくは５０質量％以上、より好ましくは６０質量％以上、特に好ましくは７０質量％以上である。 The resin composition preferably contains an epoxy resin having two or more epoxy groups in one molecule as the (B) epoxy resin. From the viewpoint of remarkably obtaining the desired effect of the present invention, the ratio of the epoxy resin having two or more epoxy groups in one molecule is preferably 50% by mass with respect to 100% by mass of the non-volatile component of the epoxy resin (B). % Or more, more preferably 60% by mass or more, and particularly preferably 70% by mass or more.
　エポキシ樹脂には、温度２５℃で液状のエポキシ樹脂（以下「液状エポキシ樹脂」ということがある。）と、温度２５℃で固体状のエポキシ樹脂（以下「固体状エポキシ樹脂」ということがある。）とがある。一実施形態では、本発明の樹脂組成物は、エポキシ樹脂として、液状エポキシ樹脂を含む。一実施形態では、本発明の樹脂組成物は、エポキシ樹脂として、固体状エポキシ樹脂を含む。本発明の樹脂組成物は、エポキシ樹脂として、液状エポキシ樹脂のみを含んでいてもよく、或いは固体状エポキシ樹脂のみを含んでいてもよく、液状エポキシ樹脂と固体状エポキシ樹脂とを組み合わせて含んでいてもよいが、好適な実施形態では、液状エポキシ樹脂のみを含む。 The epoxy resin may be a liquid epoxy resin at a temperature of 25 ° C. (hereinafter sometimes referred to as “liquid epoxy resin”) or a solid epoxy resin at a temperature of 25 ° C. (hereinafter referred to as “solid epoxy resin”). ). In one embodiment, the resin composition of the present invention comprises a liquid epoxy resin as the epoxy resin. In one embodiment, the resin composition of the present invention comprises a solid epoxy resin as the epoxy resin. The resin composition of the present invention may contain only the liquid epoxy resin or only the solid epoxy resin as the epoxy resin, and may contain a combination of the liquid epoxy resin and the solid epoxy resin. However, in a preferred embodiment, only the liquid epoxy resin is included.
　液状エポキシ樹脂としては、１分子中に２個以上のエポキシ基を有する液状エポキシ樹脂が好ましい。 As the liquid epoxy resin, a liquid epoxy resin having two or more epoxy groups in one molecule is preferable.
　液状エポキシ樹脂としては、グリシロール型エポキシ樹脂、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ＡＦ型エポキシ樹脂、ナフタレン型エポキシ樹脂、グリシジルエステル型エポキシ樹脂、グリシジルアミン型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、エステル骨格を有する脂環式エポキシ樹脂、シクロヘキサン型エポキシ樹脂、シクロヘキサンジメタノール型エポキシ樹脂、及びブタジエン構造を有するエポキシ樹脂が好ましく、グリシロール型エポキシ樹脂、ビスフェノールＡ型エポキシ樹脂、及びビスフェノールＦ型エポキシ樹脂がより好ましい。 Examples of the liquid epoxy resin include glycyrrole type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, glycidylamine type epoxy resin, and phenol novolac type epoxy. A resin, an alicyclic epoxy resin having an ester skeleton, a cyclohexane type epoxy resin, a cyclohexanedimethanol type epoxy resin, and an epoxy resin having a butadiene structure are preferable, and a glycylol type epoxy resin, a bisphenol A type epoxy resin, and a bisphenol F type epoxy are preferable. Resin is more preferred.
　液状エポキシ樹脂の具体例としては、ＤＩＣ社製の「ＨＰ４０３２」、「ＨＰ４０３２Ｄ」、「ＨＰ４０３２ＳＳ」（ナフタレン型エポキシ樹脂）；三菱ケミカル社製の「８２８ＵＳ」、「８２８ＥＬ」、「ｊＥＲ８２８ＥＬ」、「８２５」、「エピコート８２８ＥＬ」（ビスフェノールＡ型エポキシ樹脂）；三菱ケミカル社製の「ｊＥＲ８０７」、「１７５０」（ビスフェノールＦ型エポキシ樹脂）；三菱ケミカル社製の「ｊＥＲ１５２」（フェノールノボラック型エポキシ樹脂）；三菱ケミカル社製の「６３０」、「６３０ＬＳＤ」（グリシジルアミン型エポキシ樹脂）；ＡＤＥＫＡ社製の「ＥＤ－５２３Ｔ」（グリシロール型エポキシ樹脂（アデカグリシロール））、「ＥＰ－３９８０Ｓ」（グリシジルアミン型エポキシ樹脂）、「ＥＰ－４０８８Ｓ」（ジシクロペンタジエン型エポキシ樹脂）；新日鉄住金化学社製の「ＺＸ－１０５９」（ビスフェノールＡ型エポキシ樹脂とビスフェノールＦ型エポキシ樹脂の混合品）；ナガセケムテックス社製の「ＥＸ－７２１」（グリシジルエステル型エポキシ樹脂）；ダイセル社製の「セロキサイド２０２１Ｐ」（エステル骨格を有する脂環式エポキシ樹脂）；ダイセル社製の「ＰＢ－３６００」、日本曹達社製の「ＪＰ－１００」、「ＪＰ－２００」（ブタジエン構造を有するエポキシ樹脂）；新日鉄住金化学社製の「ＺＸ１６５８」、「ＺＸ１６５８ＧＳ」（液状１，４－グリシジルシクロヘキサン型エポキシ樹脂）等が挙げられる。これらは、１種類単独で用いてもよく、２種類以上を組み合わせて用いてもよい。 Specific examples of the liquid epoxy resin include "HP4032", "HP4032D", and "HP4032SS" (naphthalene type epoxy resin) manufactured by DIC; "828US", "828EL", "jER828EL", and "825" manufactured by Mitsubishi Chemical Co., Ltd. , "Epicoat 828EL" (bisphenol A type epoxy resin); "jER807", "1750" (bisphenol F type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd .; "jER152" (phenol novolac type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd.; Mitsubishi Chemical's "630" and "630LSD" (glycidylamine type epoxy resin); ADEKA's "ED-523T" (glycylol type epoxy resin (adecaglycylol)), "EP-3980S" (glycidylamine type) Epoxy resin), "EP-4088S" (dicyclopentadiene type epoxy resin); "ZX-1059" manufactured by Nippon Steel & Sumitomo Metal Corporation (mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin); Nagase ChemteX Corporation "EX-721" (glycidyl ester type epoxy resin); "Selokiside 2021P" (alicyclic epoxy resin having an ester skeleton) manufactured by Daicel Co., Ltd .; "PB-3600" manufactured by Daicel Co., Ltd., manufactured by Nippon Soda Co., Ltd. "JP-100", "JP-200" (epoxy resin having a butadiene structure); "ZX1658", "ZX1658GS" (liquid 1,4-glycidylcyclohexane type epoxy resin) manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd. and the like can be mentioned. These may be used individually by 1 type, and may be used in combination of 2 or more types.
　固体状エポキシ樹脂としては、１分子中に３個以上のエポキシ基を有する固体状エポキシ樹脂が好ましく、１分子中に３個以上のエポキシ基を有する芳香族系の固体状エポキシ樹脂がより好ましい。 As the solid epoxy resin, a solid epoxy resin having 3 or more epoxy groups in one molecule is preferable, and an aromatic solid epoxy resin having 3 or more epoxy groups in one molecule is more preferable.
　固体状エポキシ樹脂としては、ビキシレノール型エポキシ樹脂、ナフタレン型エポキシ樹脂、ナフタレン型４官能エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、ジシクロペンタジエン型エポキシ樹脂、トリスフェノール型エポキシ樹脂、ナフトール型エポキシ樹脂、ビフェニル型エポキシ樹脂、ナフチレンエーテル型エポキシ樹脂、アントラセン型エポキシ樹脂、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、テトラフェニルエタン型エポキシ樹脂が好ましい。 Examples of the solid epoxy resin include bixilenol type epoxy resin, naphthalene type epoxy resin, naphthalene type tetrafunctional epoxy resin, cresol novolac type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, naphthol type epoxy resin, and biphenyl. Type epoxy resin, naphthylene ether type epoxy resin, anthracene type epoxy resin, bisphenol A type epoxy resin, bisphenol AF type epoxy resin, and tetraphenylethane type epoxy resin are preferable.
　固体状エポキシ樹脂の具体例としては、ＤＩＣ社製の「ＨＰ４０３２Ｈ」（ナフタレン型エポキシ樹脂）；ＤＩＣ社製の「ＨＰ－４７００」、「ＨＰ－４７１０」（ナフタレン型４官能エポキシ樹脂）；ＤＩＣ社製の「Ｎ－６９０」（クレゾールノボラック型エポキシ樹脂）；ＤＩＣ社製の「Ｎ－６９５」（クレゾールノボラック型エポキシ樹脂）；ＤＩＣ社製の「ＨＰ－７２００」、「ＨＰ－７２００ＨＨ」、「ＨＰ－７２００Ｈ」（ジシクロペンタジエン型エポキシ樹脂）；ＤＩＣ社製の「ＥＸＡ－７３１１」、「ＥＸＡ－７３１１－Ｇ３」、「ＥＸＡ－７３１１－Ｇ４」、「ＥＸＡ－７３１１－Ｇ４Ｓ」、「ＨＰ６０００」（ナフチレンエーテル型エポキシ樹脂）；日本化薬社製の「ＥＰＰＮ－５０２Ｈ」（トリスフェノール型エポキシ樹脂）；日本化薬社製の「ＮＣ７０００Ｌ」（ナフトールノボラック型エポキシ樹脂）；日本化薬社製の「ＮＣ３０００Ｈ」、「ＮＣ３０００」、「ＮＣ３０００Ｌ」、「ＮＣ３１００」（ビフェニル型エポキシ樹脂）；新日鉄住金化学社製の「ＥＳＮ４７５Ｖ」（ナフトール型エポキシ樹脂）；新日鉄住金化学社製の「ＥＳＮ４８５」（ナフトールノボラック型エポキシ樹脂）；三菱ケミカル社製の「ＹＸ４０００Ｈ」、「ＹＸ４０００」、「ＹＬ６１２１」（ビフェニル型エポキシ樹脂）；三菱ケミカル社製の「ＹＸ４０００ＨＫ」（ビキシレノール型エポキシ樹脂）；三菱ケミカル社製の「ＹＸ８８００」（アントラセン型エポキシ樹脂）；三菱ケミカル社製の「ＹＸ７７００」（キシレン構造含有ノボラック型エポキシ樹脂）；大阪ガスケミカル社製の「ＰＧ－１００」、「ＣＧ－５００」；三菱ケミカル社製の「ＹＬ７７６０」（ビスフェノールＡＦ型エポキシ樹脂）；三菱ケミカル社製の「ＹＬ７８００」（フルオレン型エポキシ樹脂）；三菱ケミカル社製の「ｊＥＲ１０１０」（固体状ビスフェノールＡ型エポキシ樹脂）；三菱ケミカル社製の「ｊＥＲ１０３１Ｓ」（テトラフェニルエタン型エポキシ樹脂）等が挙げられる。これらは、１種類単独で用いてもよく、２種類以上を組み合わせて用いてもよい。 Specific examples of the solid epoxy resin include "HP4032H" (naphthalene type epoxy resin) manufactured by DIC; "HP-4700" and "HP-4710" (naphthalene type tetrafunctional epoxy resin) manufactured by DIC; DIC. "N-690" (cresol novolac type epoxy resin); DIC "N-695" (cresol novolac type epoxy resin); DIC "HP-7200", "HP-7200HH", "HP" -7200H (dicyclopentadiene type epoxy resin); DIC's "EXA-7311", "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S", "HP6000" ( Naphthylene ether type epoxy resin); "EPPN-502H" (trisphenol type epoxy resin) manufactured by Nippon Kayakusha; "NC7000L" (naphthol novolac type epoxy resin) manufactured by Nihon Kayakusha; "NC3000H", "NC3000", "NC3000L", "NC3100" (biphenyl type epoxy resin); "ESN475V" (naphthol type epoxy resin) manufactured by Nippon Steel & Sumitomo Metal Corporation; "ESN485" (naphthol novolac) manufactured by Nippon Steel & Sumitomo Metal Corporation Type epoxy resin); "YX4000H", "YX4000", "YL6121" (biphenyl type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd .; "YX4000HK" (bixilenol type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd .; "YX8800" (anthracene type epoxy resin); "YX7700" (xylene structure-containing novolac type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd .; "PG-100" and "CG-500" manufactured by Osaka Gas Chemical Co., Ltd .; "YL7760" (bisphenol AF type epoxy resin); "YL7800" (fluorene type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd .; "jER1010" (solid bisphenol A type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd .; "jER1031S" (tetraphenylethane type epoxy resin) and the like can be mentioned. These may be used individually by 1 type, and may be used in combination of 2 or more types.
　（Ｂ）エポキシ樹脂として液状エポキシ樹脂と固体状エポキシ樹脂とを組み合わせて用いる場合、液状エポキシ樹脂の固体状エポキシ樹脂に対する質量比（液状エポキシ樹脂／固体状エポキシ樹脂）は、好ましくは１以上、より好ましくは１０以上、特に好ましくは５０以上である。 (B) When a liquid epoxy resin and a solid epoxy resin are used in combination as the epoxy resin, the mass ratio of the liquid epoxy resin to the solid epoxy resin (liquid epoxy resin / solid epoxy resin) is preferably 1 or more. It is preferably 10 or more, and particularly preferably 50 or more.
　（Ｂ）エポキシ樹脂のエポキシ当量は、好ましくは５０ｇ／ｅｑ．～５０００ｇ／ｅｑ．、より好ましくは５０ｇ／ｅｑ．～３０００ｇ／ｅｑ．、さらに好ましくは８０ｇ／ｅｑ．～２０００ｇ／ｅｑ．、さらにより好ましくは１１０ｇ／ｅｑ．～１０００ｇ／ｅｑ．である。この範囲となることで、磁性シートの磁性硬化物の架橋密度が十分となり、表面粗さの小さい絶縁層をもたらすことができる。エポキシ当量は、１当量のエポキシ基を含む樹脂の質量である。このエポキシ当量は、ＪＩＳ　Ｋ７２３６に従って測定することができる。 The epoxy equivalent of the (B) epoxy resin is preferably 50 g / eq. ~ 5000g / eq. , More preferably 50 g / eq. ~ 3000g / eq. , More preferably 80 g / eq. ~ 2000g / eq. , Even more preferably 110 g / eq. ~ 1000g / eq. Is. Within this range, the crosslink density of the magnetically cured product of the magnetic sheet becomes sufficient, and an insulating layer having a small surface roughness can be provided. Epoxy equivalent is the mass of a resin containing 1 equivalent of an epoxy group. This epoxy equivalent can be measured according to JIS K7236.
　（Ｂ）エポキシ樹脂の重量平均分子量（Ｍｗ）は、本発明の所望の効果を顕著に得る観点から、好ましくは１００～５０００、より好ましくは２５０～３０００、さらに好ましくは４００～１５００である。樹脂の重量平均分子量は、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）法により、ポリスチレン換算の値として測定できる。 (B) The weight average molecular weight (Mw) of the epoxy resin is preferably 100 to 5000, more preferably 250 to 3000, and further preferably 400 to 1500 from the viewpoint of remarkably obtaining the desired effect of the present invention. The weight average molecular weight of the resin can be measured as a polystyrene-equivalent value by a gel permeation chromatography (GPC) method.
　（Ｂ）エポキシ樹脂の含有量は、特に限定されるものではないが、本発明の所望の効果を顕著に得る観点から、樹脂組成物中の不揮発成分を１００質量％とした場合、好ましくは１質量％以上、より好ましくは５質量％以上、さらに好ましくは８質量％以上、特に好ましくは１０質量％以上である。その上限は、本発明の所望の効果を顕著に得る観点から、好ましくは４０質量％以下、より好ましくは３０質量％以下、さらに好ましくは２５質量％以下、特に好ましくは２０質量％以下である。 The content of the epoxy resin (B) is not particularly limited, but is preferably 1 when the non-volatile component in the resin composition is 100% by mass from the viewpoint of remarkably obtaining the desired effect of the present invention. It is by mass% or more, more preferably 5% by mass or more, still more preferably 8% by mass or more, and particularly preferably 10% by mass or more. The upper limit is preferably 40% by mass or less, more preferably 30% by mass or less, still more preferably 25% by mass or less, and particularly preferably 20% by mass or less, from the viewpoint of remarkably obtaining the desired effect of the present invention.
＜（Ｃ）脂環式エポキシ基を有するシロキサン化合物＞
　本発明の樹脂組成物は、（Ｃ）脂環式エポキシ基を有するシロキサン化合物を含む。 <(C) Siloxane compound having an alicyclic epoxy group>
The resin composition of the present invention contains (C) a siloxane compound having an alicyclic epoxy group.
　シロキサン化合物とは、シロキサン（Ｓｉ－Ｏ－Ｓｉ）結合を有する化合物をいう。本発明におけるシロキサン化合物は、環状シロキサンであっても、鎖状シロキサンであってもよい。本発明におけるシロキサン化合物は、シロキサン結合を形成するケイ素原子を、好ましくは１０個以下、より好ましくは５個以下、特に好ましくは４個以下有する。シロキサン化合物におけるケイ素原子は、全ての置換可能部位が、脂環式エポキシ基を有するか又は有さないアルキル基、アルケニル基、アリール基等の炭化水素基で置換されていることが好ましい。当該炭化水素基は、脂環式エポキシ基以外の置換基を有していてもよい。 The siloxane compound refers to a compound having a siloxane (Si—O—Si) bond. The siloxane compound in the present invention may be a cyclic siloxane or a chain siloxane. The siloxane compound in the present invention has preferably 10 or less, more preferably 5 or less, and particularly preferably 4 or less silicon atoms forming a siloxane bond. It is preferable that all the substitutable sites of the silicon atom in the siloxane compound are substituted with a hydrocarbon group such as an alkyl group, an alkenyl group, or an aryl group having or not having an alicyclic epoxy group. The hydrocarbon group may have a substituent other than the alicyclic epoxy group.
　脂環式エポキシ基とは、飽和または不飽和の脂肪族炭素環基であって、脂肪族炭素環中の－ＣＨ２－ＣＨ２－部分の異なる炭素原子に結合した２個の水素原子が１個の酸素原子に置換され、オキサシクロプロパン環を形成している基をいう。脂環式エポキシ基としては、例えば、２，３－エポキシシクロペンチル基、３，４－エポキシシクロペンチル基、２，３－エポキシシクロヘキシル基、３，４－エポキシシクロヘキシル基等の炭素原子数４～１０のエポキシシクロアルキル基等が挙げられる。本発明におけるシロキサン化合物は、脂環式エポキシ基を、好ましくは２個以上有し、また、好ましくは１０個以下、より好ましくは５個以下、特に好ましくは４個以下有する。 The alicyclic epoxy group, a saturated or an aliphatic carbon ring group unsaturated, -CH 2 -CH 2 in the aliphatic carbon ring - two hydrogen atoms bonded to a portion different carbon atoms of 1 A group that is substituted with an oxygen atom to form an oxacyclopropane ring. Examples of the alicyclic epoxy group include a 2,3-epoxycyclopentyl group, a 3,4-epoxycyclopentyl group, a 2,3-epoxycyclohexyl group, and a 3,4-epoxycyclohexyl group having 4 to 10 carbon atoms. Epoxycycloalkyl groups and the like can be mentioned. The siloxane compound in the present invention preferably has two or more alicyclic epoxy groups, preferably 10 or less, more preferably 5 or less, and particularly preferably 4 or less.
　（Ｃ）成分は、好ましくは、式（１）： The component (C) is preferably the formula (1):
Figure JPOXMLDOC01-appb-C000003
Figure JPOXMLDOC01-appb-C000003
〔式中、Ｒは、それぞれ独立して、置換又は無置換のアルキル基、置換又は無置換のアルケニル基、又は置換又は無置換のアリール基を示し、Ｘは、それぞれ独立して、置換又は無置換のアルキレン基を示し、Ｙは、それぞれ独立して、脂環式エポキシ基を示し、ｎは、１以上の整数を示し、Ｒ１及びＲ２は、それぞれ独立して、置換又は無置換のアルキル基、置換又は無置換のアルケニル基、又は置換又は無置換のアリール基を示すか、或いはＲ１及びＲ２が一緒になって１個の－Ｏ－を示して互いに結合し、環状シロキサンを形成する。〕
で表される化合物である。 [In the formula, R independently represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a substituted or unsubstituted aryl group, and X is independently substituted or unsubstituted, respectively. Substituted alkylene groups, Y each independently represents an alicyclic epoxy group, n represents an integer greater than or equal to 1, and R 1 and R 2 are independently substituted or unsubstituted, respectively. An alkyl group, a substituted or unsubstituted alkenyl group, or a substituted or unsubstituted aryl group is shown, or R 1 and R 2 are combined to show one —O— and bonded to each other to form a cyclic siloxane. Form. ]
It is a compound represented by.
　式（１）において、Ｒは、それぞれ独立して、置換又は無置換のアルキル基、置換又は無置換のアルケニル基、又は置換又は無置換のアリール基を示し、好ましくは、置換又は無置換のアルキル基であり、より好ましくは（無置換）アルキル基であり、特に好ましくはメチル基又はエチル基である。Ｘは、それぞれ独立して、置換又は無置換のアルキレン基を示し、好ましくは、（無置換）アルキレン基であり、特に好ましくは、－ＣＨ２－、又は－ＣＨ２－ＣＨ２－である。Ｙは、それぞれ独立して、脂環式エポキシ基を示し、好ましくは、炭素原子数４～１０のエポキシシクロアルキル基であり、特に好ましくは、３，４－エポキシシクロヘキシル基である。ｎは、１以上の整数を示し、好ましくは１～９の整数であり、より好ましくは１～４の整数であり、特に好ましくは１～３の整数である。Ｒ１及びＲ２は、それぞれ独立して、置換又は無置換のアルキル基、置換又は無置換のアルケニル基、又は置換又は無置換のアリール基を示すか、好ましくは、置換又は無置換のアルキル基であるか、より好ましくは、（無置換）アルキル基であるか、特に好ましくはメチル基又はエチル基であるか、或いは、Ｒ１及びＲ２が一緒になって１個の－Ｏ－を示して互いに結合し、環状シロキサンを形成する。また、Ｒ１及びＲ２が一緒になって１個の－Ｏ－を示して互いに結合し、環状シロキサンを形成する場合は、ｎが、２以上であることが好ましい。 In formula (1), R independently represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a substituted or unsubstituted aryl group, preferably a substituted or unsubstituted alkyl. It is a group, more preferably a (unsubstituted) alkyl group, and particularly preferably a methyl group or an ethyl group. X independently represents a substituted or unsubstituted alkylene group, preferably a (unsubstituted) alkylene group, and particularly preferably -CH 2- or -CH 2- CH 2- . Y represents an alicyclic epoxy group independently of each other, and is preferably an epoxycycloalkyl group having 4 to 10 carbon atoms, and particularly preferably a 3,4-epoxycyclohexyl group. n represents an integer of 1 or more, preferably an integer of 1 to 9, more preferably an integer of 1 to 4, and particularly preferably an integer of 1 to 3. R 1 and R 2 independently represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a substituted or unsubstituted aryl group, or preferably a substituted or unsubstituted alkyl group. , More preferably an (unsubstituted) alkyl group, particularly preferably a methyl or ethyl group, or R 1 and R 2 together to indicate one —O—. To bond with each other to form cyclic siloxane. Further, when R 1 and R 2 are combined to indicate one —O— and bonded to each other to form a cyclic siloxane, n is preferably 2 or more.
　「アルキル基」とは、直鎖、分枝鎖又は環状の１価の脂肪族飽和炭化水素基をいう。「アルキル基」は、炭素原子数１～６のアルキル基が好ましく、炭素原子数１～３のアルキル基がより好ましい。「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、ブチル基、イソブチル基、ｓｅｃ－ブチル基、ｔｅｒｔ－ブチル基、ペンチル基、イソペンチル基、ネオペンチル基、シクロペンチル基、シクロヘキシル基等が挙げられ、好ましくは、メチル基、及びエチル基である。「アルケニル基」とは、少なくとも１つの炭素－炭素二重結合を有する直鎖、分枝鎖又は環状の１価の脂肪族不飽和炭化水素基をいう。「アルケニル基」は、炭素原子数２～６のアルケニル基が好ましく、炭素原子数２又は３のアルケニル基がより好ましい。「アルケニル基」としては、例えば、ビニル基、１－プロペニル基、２－プロペニル基、２－メチル－１－プロペニル基、１－ブテニル基、２－ブテニル基、３－ブテニル基、３－メチル－２－ブテニル基、１－ペンテニル基、２－ペンテニル基、３－ペンテニル基、４－ペンテニル基、４－メチル－３－ペンテニル基、１－ヘキセニル基、３－ヘキセニル基、５－ヘキセニル基、２－シクロヘキセニル基等が挙げられる。「アルキレン基」とは、直鎖、分枝鎖又は環状の２価の脂肪族飽和炭化水素基をいう。「アルキレン基」は、炭素原子数１～６のアルキレン基が好ましく、炭素原子数１～３のアルキレン基がより好ましい。「アルキレン基」としては、例えば、－ＣＨ２－、－ＣＨ２－ＣＨ２－、－ＣＨ（ＣＨ３）－、－ＣＨ２－ＣＨ２－ＣＨ２－、－ＣＨ２－ＣＨ（ＣＨ３）－、－ＣＨ（ＣＨ３）－ＣＨ２－、－Ｃ（ＣＨ３）２－、－ＣＨ２－ＣＨ２－ＣＨ２－ＣＨ２－、－ＣＨ２－ＣＨ２－ＣＨ（ＣＨ３）－、－ＣＨ２－ＣＨ（ＣＨ３）－ＣＨ２－、－ＣＨ（ＣＨ３）－ＣＨ２－ＣＨ２－、－ＣＨ２－Ｃ（ＣＨ３）２－、－Ｃ（ＣＨ３）２－ＣＨ２－等が挙げられ、好ましくは、－ＣＨ２－、又は－ＣＨ２－ＣＨ２－である。「置換又は無置換のアルキル基」におけるアルキル基、「置換又は無置換のアルケニル基」におけるアルケニル基、及び「置換又は無置換のアルキレン基」におけるアルキレン基の置換基としては、特に限定されるものではないが、例えば、ハロゲン原子、シアノ基、アルコキシ基、アルキルカルボニル基、アリール基、ヘテロアリール基、アリールオキシ基、アリールカルボニル基、アミノ基、ニトロ基、ヒドロキシ基等、又はこれらを組み合わせた基が挙げられる。置換基数としては、１～３個であることが好ましく、１個であることがより好ましい。 The "alkyl group" refers to a linear, branched or cyclic monovalent aliphatic saturated hydrocarbon group. The "alkyl group" is preferably an alkyl group having 1 to 6 carbon atoms, and more preferably an alkyl group having 1 to 3 carbon atoms. Examples of the "alkyl group" include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, cyclopentyl group and cyclohexyl. Examples thereof include a methyl group and an ethyl group. The "alkenyl group" refers to a linear, branched or cyclic monovalent aliphatic unsaturated hydrocarbon group having at least one carbon-carbon double bond. The "alkenyl group" is preferably an alkenyl group having 2 to 6 carbon atoms, and more preferably an alkenyl group having 2 or 3 carbon atoms. Examples of the "alkenyl group" include vinyl group, 1-propenyl group, 2-propenyl group, 2-methyl-1-propenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group and 3-methyl-. 2-butenyl group, 1-pentenyl group, 2-pentenyl group, 3-pentenyl group, 4-pentenyl group, 4-methyl-3-pentenyl group, 1-hexenyl group, 3-hexenyl group, 5-hexenyl group, 2 -Includes cyclohexenyl groups and the like. The "alkylene group" refers to a linear, branched or cyclic divalent aliphatic saturated hydrocarbon group. The "alkylene group" is preferably an alkylene group having 1 to 6 carbon atoms, and more preferably an alkylene group having 1 to 3 carbon atoms. The "alkylene group", for example, -CH 2 -, - CH 2 -CH 2 -, - CH (CH 3) -, - CH 2 -CH 2 -CH 2 -, - CH 2 -CH (CH 3) -, - CH (CH 3) -CH 2 -, - C (CH 3) 2 -, - CH 2 -CH 2 -CH 2 -CH 2 -, - CH 2 -CH 2 -CH (CH 3) -, -CH 2 -CH (CH 3) -CH 2 -, - CH (CH 3) -CH 2 -CH 2 -, - CH 2 -C (CH 3) 2 -, - C (CH 3) 2 -CH 2 -Etc., preferably -CH 2- or -CH 2- CH 2- . The alkyl group in the "substituted or unsubstituted alkyl group", the alkenyl group in the "substituted or unsubstituted alkenyl group", and the substituent of the alkylene group in the "substituted or unsubstituted alkylene group" are particularly limited. Although not, for example, a halogen atom, a cyano group, an alkoxy group, an alkylcarbonyl group, an aryl group, a heteroaryl group, an aryloxy group, an arylcarbonyl group, an amino group, a nitro group, a hydroxy group, etc., or a group obtained by combining these. Can be mentioned. The number of substituents is preferably 1 to 3, and more preferably 1.
　「アリール基」とは、１価の芳香族炭化水素基をいう。「アリール基」は、炭素原子数６～１４のアリール基が好ましく、炭素原子数６～１０のアリール基がより好ましい。「アリール基」としては、例えば、フェニル基、１－ナフチル基、２－ナフチル基等が挙げられ、好ましくは、フェニル基である。「置換又は無置換のアリール基」におけるアリール基の置換基としては、特に限定されるものではないが、例えば、ハロゲン原子、シアノ基、アルキル基、アルコキシ基、アルキルカルボニル基、アリール基、ヘテロアリール基、アリールオキシ基、アリールカルボニル基、アラルキル基、アミノ基、ニトロ基、ヒドロキシ基等、又はこれらを組み合わせた基が挙げられる。置換基数としては、１～３個であることが好ましく、１個であることがより好ましい。 "Aryl group" refers to a monovalent aromatic hydrocarbon group. The "aryl group" is preferably an aryl group having 6 to 14 carbon atoms, and more preferably an aryl group having 6 to 10 carbon atoms. Examples of the "aryl group" include a phenyl group, a 1-naphthyl group, a 2-naphthyl group and the like, and a phenyl group is preferable. The substituent of the aryl group in the "substituted or unsubstituted aryl group" is not particularly limited, but for example, a halogen atom, a cyano group, an alkyl group, an alkoxy group, an alkylcarbonyl group, an aryl group, or a heteroaryl. Examples thereof include a group, an aryloxy group, an arylcarbonyl group, an aralkyl group, an amino group, a nitro group, a hydroxy group and the like, or a group in which these are combined. The number of substituents is preferably 1 to 3, and more preferably 1.
　「ハロゲン原子」としては、例えば、フッ素原子、塩素原子、臭素原子等が挙げられる。「アルコキシ基」とは、酸素原子にアルキル基が結合して形成される１価の基（アルキル－Ｏ－）をいう。「アルコキシ基」は、炭素原子数１～６のアルコキシ基が好ましく、炭素原子数１～３のアルコキシ基がより好ましい。「アルコキシ基」としては、例えば、メトキシ基、エトキシ基、プロポキシ基、イソプロポキシ基、ブトキシ基、イソブトキシ基、ｓｅｃ－ブトキシ基、ｔｅｒｔ－ブトキシ基、ペンチルオキシ基等が挙げられる。「アルキルカルボニル基」とは、アルキル基がカルボニルに結合して形成される１価の基（アルキル－ＣＯ－）をいう。「アルキルカルボニル基」は、炭素原子数２～７のアルキルカルボニル基が好ましく、炭素原子数２～４のアルキルカルボニル基がより好ましい。「アルキルカルボニル基」としては、例えば、アセチル基、プロパノイル基、ブタノイル基、２－メチルプロパノイル基、ペンタノイル基、３－メチルブタノイル基、２－メチルブタノイル基、２，２－ジメチルプロパノイル基、ヘキサノイル基、ヘプタノイル基等が挙げられる。 Examples of the "halogen atom" include a fluorine atom, a chlorine atom, a bromine atom and the like. The "alkoxy group" refers to a monovalent group (alkyl-O-) formed by bonding an alkyl group to an oxygen atom. The "alkoxy group" is preferably an alkoxy group having 1 to 6 carbon atoms, and more preferably an alkoxy group having 1 to 3 carbon atoms. Examples of the "alkoxy group" include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group, a sec-butoxy group, a tert-butoxy group, a pentyloxy group and the like. The "alkylcarbonyl group" refers to a monovalent group (alkyl-CO-) formed by bonding an alkyl group to a carbonyl. The "alkylcarbonyl group" is preferably an alkylcarbonyl group having 2 to 7 carbon atoms, and more preferably an alkylcarbonyl group having 2 to 4 carbon atoms. Examples of the "alkylcarbonyl group" include an acetyl group, a propanoyl group, a butanoyl group, a 2-methylpropanol group, a pentanoyl group, a 3-methylbutanoyl group, a 2-methylbutanoyl group, and a 2,2-dimethylpropanoyl. Examples include a group, a hexanoyl group, a heptanoyle group and the like.
　「ヘテロアリール基」とは、環構成原子として、炭素原子以外に、酸素原子、窒素原子及び硫黄原子から選ばれる１ないし４個のヘテロ原子を有する１価の芳香族複素環基をいう。「ヘテロアリール基」は、５ないし１２員（好ましくは５又は６員）の単環式、二環式又は三環式（好ましくは単環式）芳香族複素環基が好ましい。「ヘテロアリール基」としては、例えば、フリル基、チエニル基、ピロリル基、オキサゾリル基、イソオキサゾリル基、チアゾリル基、イソチアゾリル基、イミダゾリル基、ピラゾリル基、１，２，３－オキサジアゾリル基、１，２，４－オキサジアゾリル基、１，３，４－オキサジアゾリル基、フラザニル基、１，２，３－チアジアゾリル基、１，２，４－チアジアゾリル基、１，３，４－チアジアゾリル基、１，２，３－トリアゾリル基、１，２，４－トリアゾリル基、テトラゾリル基、ピリジル基、ピリダジニル基、ピリミジニル基、ピラジニル基、トリアジニル基等が挙げられる。 The "heteroaryl group" refers to a monovalent aromatic heterocyclic group having 1 to 4 heteroatoms selected from an oxygen atom, a nitrogen atom and a sulfur atom in addition to a carbon atom as a ring-constituting atom. The "heteroaryl group" is preferably a 5- to 12-membered (preferably 5- or 6-membered) monocyclic, bicyclic or tricyclic (preferably monocyclic) aromatic heterocyclic group. Examples of the "heteroaryl group" include a frill group, a thienyl group, a pyrrolyl group, an oxazolyl group, an isooxazolyl group, a thiazolyl group, an isothiazolyl group, an imidazolyl group, a pyrazolyl group, 1,2,3-oxadiazolyl group, 1,2, 4-Oxaziazolyl group, 1,3,4-oxadiazolyl group, Frazanyl group, 1,2,3-thiadiazolyl group, 1,2,4-thiadiazolyl group, 1,3,4-thiadiazolyl group, 1,2,3- Examples thereof include a triazolyl group, a 1,2,4-triazolyl group, a tetrazolyl group, a pyridyl group, a pyridadinyl group, a pyrimidinyl group, a pyrazinyl group and a triazinyl group.
　「アリールオキシ基」とは、アリール基が酸素原子に結合して形成される１価の基（アリール－Ｏ－）をいう。「アリールオキシ基」は、炭素原子数６～１４のアリールオキシ基が好ましく、炭素原子数６～１０のアリールオキシ基がより好ましい。「アリールオキシ基」としては、例えば、フェノキシ基、ナフトキシ基等が挙げられる。「アリールカルボニル基」とは、アリール基がカルボニルに結合して形成される１価の基（アリール－ＣＯ－）をいう。「アリールカルボニル基」は、炭素原子数７～１５のアリールカルボニル基が好ましく、炭素原子数７～１１のアリールカルボニル基がより好ましい。「アリールカルボニル基」としては、例えば、ベンゾイル基、１－ナフトイル基、２－ナフトイル基等が挙げられる。「アラルキル基」とは、１又は２個以上のアリール基で置換されたアルキル基をいう。「アラルキル基」は、炭素原子数７～１５のアラルキル基が好ましく、炭素原子数７～１１のアラルキル基がより好ましい。「アラルキル基」としては、例えば、ベンジル基、フェネチル基、２－ナフチルメチル基等が挙げられる。 The "aryloxy group" refers to a monovalent group (aryl-O-) formed by bonding an aryl group to an oxygen atom. The "aryloxy group" is preferably an aryloxy group having 6 to 14 carbon atoms, and more preferably an aryloxy group having 6 to 10 carbon atoms. Examples of the "aryloxy group" include a phenoxy group and a naphthoxy group. The "arylcarbonyl group" refers to a monovalent group (aryl-CO-) formed by bonding an aryl group to a carbonyl. The "arylcarbonyl group" is preferably an arylcarbonyl group having 7 to 15 carbon atoms, and more preferably an arylcarbonyl group having 7 to 11 carbon atoms. Examples of the "arylcarbonyl group" include a benzoyl group, a 1-naphthoyl group, a 2-naphthoyl group and the like. The "aralkyl group" refers to an alkyl group substituted with one or more aryl groups. The "aralkyl group" is preferably an aralkyl group having 7 to 15 carbon atoms, and more preferably an aralkyl group having 7 to 11 carbon atoms. Examples of the "aralkyl group" include a benzyl group, a phenethyl group, a 2-naphthylmethyl group and the like.
　（Ｃ）成分の分子量は、好ましくは２，０００以下、より好ましくは１，５００以下、さらに好ましくは１，０００以下、特に好ましくは８００以下である。下限は、例えば、２００以上等とし得る。 The molecular weight of the component (C) is preferably 2,000 or less, more preferably 1,500 or less, still more preferably 1,000 or less, and particularly preferably 800 or less. The lower limit may be, for example, 200 or more.
　（Ｃ）成分のエポキシ当量は、好ましくは５０ｇ／ｅｑ．～１０００ｇ／ｅｑ．、より好ましくは１００ｇ／ｅｑ．～５００ｇ／ｅｑ．、さらに好ましくは１５０ｇ／ｅｑ．～３００ｇ／ｅｑ．、特に好ましくは１５０ｇ／ｅｑ．～２５０ｇ／ｅｑ．である。 The epoxy equivalent of the component (C) is preferably 50 g / eq. ~ 1000g / eq. , More preferably 100 g / eq. ~ 500 g / eq. , More preferably 150 g / eq. ~ 300 g / eq. , Particularly preferably 150 g / eq. ~ 250 g / eq. Is.
　（Ｃ）成分の具体例としては、信越化学社製の「ＫＲ－４７０」（主成分：２，４，６，８－テトラキス（２－（３，４－エポキシシクロヘキシル）エチル）－２，４，６，８－テトラメチルシクロテトラシロキサン）、「Ｘ－４０－２６６７」（主成分：１，３，５－トリス（２－（３，４－エポキシシクロヘキシル）エチル）－１，１，３，５，５－ペンタメチルトリシロキサン）、「Ｘ－４０－２７１５」（主成分：１，３－ビス（２－（３，４－エポキシシクロヘキシル）エチル）－１，１，３，３－テトラメチルジシロキサン）などが挙げられる。これらは、１種類単独で用いてもよく、２種類以上を組み合わせて用いてもよい。 As a specific example of the component (C), "KR-470" manufactured by Shin-Etsu Chemical Co., Ltd. (main component: 2,4,6,8-tetraxane (2- (3,4-epoxycyclohexane) ethyl) -2,4 , 6,8-Tetramethylcyclotetrasiloxane), "X-40-2667" (main component: 1,3,5-tris (2- (3,4-epoxycyclohexyl) ethyl) -1,1,3 5,5-Pentamethyltrisiloxane), "X-40-2715" (main component: 1,3-bis (2- (3,4-epoxycyclohexyl) ethyl) -1,1,3,3-tetramethyl Disiloxane) and the like. These may be used individually by 1 type, and may be used in combination of 2 or more types.
　（Ｃ）成分の含有量は、特に限定されるものではないが、本発明の所望の効果を顕著に得る観点から、樹脂組成物中の不揮発成分を１００質量％とした場合、好ましくは０．１質量％以上、より好ましくは１質量％以上、さらに好ましくは２質量％以上、特に好ましくは３質量％以上である。その上限は、本発明の所望の効果を顕著に得る観点から、好ましくは５０質量％以下、より好ましくは３０質量％以下、さらに好ましくは２０質量％以下、特に好ましくは１５質量％以下である。 The content of the component (C) is not particularly limited, but from the viewpoint of remarkably obtaining the desired effect of the present invention, when the non-volatile component in the resin composition is 100% by mass, it is preferably 0. It is 1% by mass or more, more preferably 1% by mass or more, still more preferably 2% by mass or more, and particularly preferably 3% by mass or more. The upper limit is preferably 50% by mass or less, more preferably 30% by mass or less, still more preferably 20% by mass or less, and particularly preferably 15% by mass or less, from the viewpoint of remarkably obtaining the desired effect of the present invention.
＜（Ｄ）硬化剤＞
　本発明の樹脂組成物は、任意成分として（Ｄ）硬化剤を含む場合がある。（Ｄ）硬化剤を含有させることで（Ｂ）エポキシ樹脂をより容易に硬化できる。 <(D) Hardener>
The resin composition of the present invention may contain (D) a curing agent as an optional component. By containing (D) a curing agent, (B) the epoxy resin can be cured more easily.
　（Ｄ）硬化剤には、（Ｂ）エポキシ樹脂を硬化する機能を有するエポキシ樹脂硬化剤と、（Ｂ）エポキシ樹脂の硬化を促進させる機能を有する硬化促進剤とがある。（Ｄ）硬化剤として、エポキシ樹脂硬化剤及び硬化促進剤のいずれかを含むことが好ましく、エポキシ樹脂硬化剤を含むことがより好ましい。 The (D) curing agent includes (B) an epoxy resin curing agent having a function of curing the epoxy resin and (B) a curing accelerator having a function of accelerating the curing of the epoxy resin. (D) The curing agent preferably contains either an epoxy resin curing agent or a curing accelerator, and more preferably contains an epoxy resin curing agent.
［エポキシ樹脂硬化剤］
　エポキシ樹脂硬化剤としては、エポキシ樹脂を硬化する機能を有する限り特に限定されず、例えば、フェノール系硬化剤、ナフトール系硬化剤、酸無水物系硬化剤、活性エステル系硬化剤、ベンゾオキサジン系硬化剤、シアネートエステル系硬化剤、カルボジイミド系硬化剤、イミダゾール系硬化剤等が挙げられる。エポキシ樹脂硬化剤としては、酸無水物系硬化剤およびイミダゾール系硬化剤が好ましく、特にイミダゾール系硬化剤が好ましい。エポキシ樹脂硬化剤は１種単独で用いてもよく、又は２種以上を併用してもよい。 [Epoxy resin curing agent]
The epoxy resin curing agent is not particularly limited as long as it has a function of curing the epoxy resin. For example, a phenol-based curing agent, a naphthol-based curing agent, an acid anhydride-based curing agent, an active ester-based curing agent, and a benzoxazine-based curing agent. Examples thereof include agents, cyanate ester-based curing agents, carbodiimide-based curing agents, and imidazole-based curing agents. As the epoxy resin curing agent, an acid anhydride-based curing agent and an imidazole-based curing agent are preferable, and an imidazole-based curing agent is particularly preferable. The epoxy resin curing agent may be used alone or in combination of two or more.
　フェノール系硬化剤及びナフトール系硬化剤としては、耐熱性及び耐水性の観点から、ノボラック構造を有するフェノール系硬化剤、又はノボラック構造を有するナフトール系硬化剤が好ましい。また、被着体に対する密着性の観点から、含窒素フェノール系硬化剤又は含窒素ナフトール系硬化剤が好ましく、トリアジン骨格含有フェノール系硬化剤又はトリアジン骨格含有ナフトール系硬化剤がより好ましい。中でも、耐熱性、耐水性、及び密着性を高度に満足させる観点から、トリアジン骨格含有フェノールノボラック樹脂が好ましい。フェノール系硬化剤及びナフトール系硬化剤の具体例としては、例えば、明和化成社製の「ＭＥＨ－７７００」、「ＭＥＨ－７８１０」、「ＭＥＨ－７８５１」、「ＭＥＨ－８０００Ｈ」、日本化薬社製の「ＮＨＮ」、「ＣＢＮ」、「ＧＰＨ」、新日鉄住金化学社製の「ＳＮ－１７０」、「ＳＮ－１８０」、「ＳＮ－１９０」、「ＳＮ－４７５」、「ＳＮ－４８５」、「ＳＮ－４９５」、「ＳＮ－３７５」、「ＳＮ－３９５」、ＤＩＣ社製の「ＬＡ－７０５２」、「ＬＡ－７０５４」、「ＬＡ－３０１８」、「ＬＡ－３０１８－５０Ｐ」、「ＬＡ－１３５６」、「ＴＤ２０９０」等が挙げられる。 As the phenol-based curing agent and the naphthol-based curing agent, a phenol-based curing agent having a novolak structure or a naphthol-based curing agent having a novolak structure is preferable from the viewpoint of heat resistance and water resistance. Further, from the viewpoint of adhesion to the adherend, a nitrogen-containing phenol-based curing agent or a nitrogen-containing naphthol-based curing agent is preferable, and a triazine skeleton-containing phenol-based curing agent or a triazine skeleton-containing naphthol-based curing agent is more preferable. Of these, a triazine skeleton-containing phenol novolac resin is preferable from the viewpoint of highly satisfying heat resistance, water resistance, and adhesion. Specific examples of the phenol-based curing agent and the naphthol-based curing agent include, for example, "MEH-7700", "MEH-7810", "MEH-7851", "MEH-8000H" manufactured by Meiwa Kasei Co., Ltd., and Nippon Kayaku Co., Ltd. "NHN", "CBN", "GPH" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. "SN-170", "SN-180", "SN-190", "SN-475", "SN-485", "SN-495", "SN-375", "SN-395", "LA-7052", "LA-7054", "LA-3018", "LA-3018-50P", "LA" manufactured by DIC. -1356 ”,“ TD2090 ”and the like.
　酸無水物系硬化剤としては、１分子内中に１個以上の酸無水物基を有する硬化剤が挙げられる。酸無水物系硬化剤の具体例としては、無水フタル酸、テトラヒドロ無水フタル酸、ヘキサヒドロ無水フタル酸、メチルテトラヒドロ無水フタル酸、メチルヘキサヒドロ無水フタル酸、メチルナジック酸無水物、水素化メチルナジック酸無水物、トリアルキルテトラヒドロ無水フタル酸、ドデセニル無水コハク酸、５－（２，５－ジオキソテトラヒドロ－３－フラニル）－３－メチル－３－シクロヘキセン－１，２－ジカルボン酸無水物、無水トリメリット酸、無水ピロメリット酸、ベンソフェノンテトラカルボン酸二無水物、ビフェニルテトラカルボン酸二無水物、ナフタレンテトラカルボン酸二無水物、オキシジフタル酸二無水物、３，３’－４，４’－ジフェニルスルホンテトラカルボン酸二無水物、１，３，３ａ，４，５，９ｂ－ヘキサヒドロ－５－（テトラヒドロ－２，５－ジオキソ－３－フラニル）－ナフト［１，２－Ｃ］フラン－１，３－ジオン、エチレングリコールビス（アンヒドロトリメリテート）、メチルビシクロ［２．２．１］ヘプタン－２，３－ジカルボン酸無水物／ビシクロ［２．２．１］ヘプタン－２，３－ジカルボン酸無水物（市販品としては新日本理化社製の「ＨＮＡ－１００」）、スチレンとマレイン酸とが共重合したスチレン・マレイン酸樹脂などのポリマー型の酸無水物などが挙げられる。 Examples of the acid anhydride-based curing agent include a curing agent having one or more acid anhydride groups in one molecule. Specific examples of the acid anhydride-based curing agent include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic acid anhydride, and methylnadic hydride. Anhydride, Trialkyltetrahydrophthalic anhydride, Dodecenyl succinic anhydride, 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride, Trianhydride Merit acid, pyromellitic anhydride, benzophenone tetracarboxylic acid dianhydride, biphenyltetracarboxylic acid dianhydride, naphthalenetetracarboxylic acid dianhydride, oxydiphthalic acid dianhydride, 3,3'-4,4'- Diphenylsulfone tetracarboxylic dianhydride, 1,3,3a,4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-franyl) -naphtho [1,2-C] furan-1 , 3-Dione, ethylene glycol bis (anhydrotrimeritate), methylbicyclo [2.2.1] heptane-2,3-dicarboxylic anhydride / bicyclo [2.2.1] heptane-2,3- Examples thereof include dicarboxylic acid anhydride (“HNA-100” manufactured by Shin Nihon Rika Co., Ltd. as a commercially available product), polymer-type acid anhydride such as styrene / maleic acid resin in which styrene and maleic acid are copolymerized.
　活性エステル系硬化剤としては、特に制限はないが、一般にフェノールエステル類、チオフェノールエステル類、Ｎ－ヒドロキシアミンエステル類、複素環ヒドロキシ化合物のエステル類等の反応活性の高いエステル基を１分子中に２個以上有する化合物が好ましく用いられる。当該活性エステル系硬化剤は、カルボン酸化合物及び／又はチオカルボン酸化合物とヒドロキシ化合物及び／又はチオール化合物との縮合反応によって得られるものが好ましい。特に耐熱性向上の観点から、カルボン酸化合物とヒドロキシ化合物とから得られる活性エステル系硬化剤が好ましく、カルボン酸化合物とフェノール化合物及び／又はナフトール化合物とから得られる活性エステル系硬化剤がより好ましい。カルボン酸化合物としては、例えば安息香酸、酢酸、コハク酸、マレイン酸、イタコン酸、フタル酸、イソフタル酸、テレフタル酸、ピロメリット酸等が挙げられる。フェノール化合物又はナフトール化合物としては、例えば、ハイドロキノン、レゾルシン、ビスフェノールＡ、ビスフェノールＦ、ビスフェノールＳ、フェノールフタリン、メチル化ビスフェノールＡ、メチル化ビスフェノールＦ、メチル化ビスフェノールＳ、フェノール、ｏ－クレゾール、ｍ－クレゾール、ｐ－クレゾール、カテコール、α－ナフトール、β－ナフトール、１，５－ジヒドロキシナフタレン、１，６－ジヒドロキシナフタレン、２，６－ジヒドロキシナフタレン、ジヒドロキシベンゾフェノン、トリヒドロキシベンゾフェノン、テトラヒドロキシベンゾフェノン、フロログルシン、ベンゼントリオール、ジシクロペンタジエン型ジフェノール化合物、フェノールノボラック等が挙げられる。ここで、「ジシクロペンタジエン型ジフェノール化合物」とは、ジシクロペンタジエン１分子にフェノール２分子が縮合して得られるジフェノール化合物をいう。 The active ester-based curing agent is not particularly limited, but generally contains an ester group having high reactive activity such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds in one molecule. A compound having two or more esters is preferably used. The active ester-based curing agent is preferably obtained by a condensation reaction between a carboxylic acid compound and / or a thiocarboxylic acid compound and a hydroxy compound and / or a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester-based curing agent obtained from a carboxylic acid compound and a hydroxy compound is preferable, and an active ester-based curing agent obtained from a carboxylic acid compound and a phenol compound and / or a naphthol compound is more preferable. Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid and the like. Examples of the phenol compound or naphthol compound include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthaline, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-. Cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenol, trihydroxybenzophenol, tetrahydroxybenzophenone, fluoroglusin, Examples thereof include benzenetriol, dicyclopentadiene-type diphenol compounds, and phenol novolac. Here, the "dicyclopentadiene-type diphenol compound" refers to a diphenol compound obtained by condensing two phenol molecules with one dicyclopentadiene molecule.
　具体的には、ジシクロペンタジエン型ジフェノール構造を含む活性エステル化合物、ナフタレン構造を含む活性エステル化合物、フェノールノボラックのアセチル化物を含む活性エステル化合物、フェノールノボラックのベンゾイル化物を含む活性エステル化合物が好ましく、中でもナフタレン構造を含む活性エステル化合物、ジシクロペンタジエン型ジフェノール構造を含む活性エステル化合物がより好ましい。「ジシクロペンタジエン型ジフェノール構造」とは、フェニレン－ジシクロペンタレン－フェニレンからなる２価の構造単位を表す。 Specifically, an active ester compound containing a dicyclopentadiene-type diphenol structure, an active ester compound containing a naphthalene structure, an active ester compound containing an acetylated product of phenol novolac, and an active ester compound containing a benzoylated product of phenol novolac are preferable. Of these, an active ester compound containing a naphthalene structure and an active ester compound containing a dicyclopentadiene-type diphenol structure are more preferable. The "dicyclopentadiene-type diphenol structure" represents a divalent structural unit composed of phenylene-dicyclopentalene-phenylene.
　活性エステル系硬化剤の市販品としては、ジシクロペンタジエン型ジフェノール構造を含む活性エステル化合物として、「ＥＸＢ９４５１」、「ＥＸＢ９４６０」、「ＥＸＢ９４６０Ｓ」、「ＨＰＣ－８０００」、「ＨＰＣ－８０００Ｈ」、「ＨＰＣ－８０００－６５Ｔ」、「ＨＰＣ－８０００Ｈ－６５ＴＭ」、「ＥＸＢ－８０００Ｌ」、「ＥＸＢ－８０００Ｌ－６５ＴＭ」（ＤＩＣ社製）；ナフタレン構造を含む活性エステル化合物として「ＥＸＢ９４１６－７０ＢＫ」、「ＥＸＢ－８１５０－６５Ｔ」（ＤＩＣ社製）；フェノールノボラックのアセチル化物を含む活性エステル化合物として「ＤＣ８０８」（三菱ケミカル社製）；フェノールノボラックのベンゾイル化物を含む活性エステル化合物として「ＹＬＨ１０２６」（三菱ケミカル社製）；フェノールノボラックのアセチル化物である活性エステル系硬化剤として「ＤＣ８０８」（三菱ケミカル社製）；フェノールノボラックのベンゾイル化物である活性エステル系硬化剤として「ＹＬＨ１０２６」（三菱ケミカル社製）、「ＹＬＨ１０３０」（三菱ケミカル社製）、「ＹＬＨ１０４８」（三菱ケミカル社製）；等が挙げられる。 Commercially available products of active ester-based curing agents include "EXB9451", "EXB9460", "EXB9460S", "HPC-8000", "HPC-8000H", and "EXB9451", "EXB9460", "EXB9460S", and "HPC-8000H" as active ester compounds containing a dicyclopentadiene type diphenol structure. HPC-8000-65T "," HPC-8000H-65TM "," EXB-8000L "," EXB-8000L-65TM "(manufactured by DIC);" EXB9416-70BK "," EXB9416-70BK "as active ester compounds containing a naphthalene structure. -8150-65T "(manufactured by DIC);" DC808 "(manufactured by Mitsubishi Chemical Co., Ltd.) as an active ester compound containing an acetylated product of phenol novolac;" YLH1026 "(manufactured by Mitsubishi Chemical Co., Ltd.) as an active ester compound containing a benzoylated product of phenol novolac. (Manufactured by); "DC808" (manufactured by Mitsubishi Chemical Co., Ltd.) as an active ester-based curing agent which is an acetylated product of phenol novolac; Examples thereof include "YLH1030" (manufactured by Mitsubishi Chemical Co., Ltd.) and "YLH1048" (manufactured by Mitsubishi Chemical Co., Ltd.).
　ベンゾオキサジン系硬化剤の具体例としては、ＪＦＥケミカル社製の「ＪＢＺ－ＯＰ１００Ｄ」、「ＯＤＡ－ＢＯＺ」；昭和高分子社製の「ＨＦＢ２００６Ｍ」、四国化成工業社製の「Ｐ－ｄ」、「Ｆ－ａ」などが挙げられる。 Specific examples of the benzoxazine-based curing agent include "JBZ-OP100D" and "ODA-BOZ" manufactured by JFE Chemical Co., Ltd .; "HFB2006M" manufactured by Showa High Polymer Co., Ltd. and "Pd" manufactured by Shikoku Chemicals Corporation. Examples include "FA".
　シアネートエステル系硬化剤としては、例えば、ビスフェノールＡジシアネート、ポリフェノールシアネート（オリゴ（３－メチレン－１，５－フェニレンシアネート））、４，４’－メチレンビス（２，６－ジメチルフェニルシアネート）、４，４’－エチリデンジフェニルジシアネート、ヘキサフルオロビスフェノールＡジシアネート、２，２－ビス（４－シアネート）フェニルプロパン、１，１－ビス（４－シアネートフェニルメタン）、ビス（４－シアネート－３，５－ジメチルフェニル）メタン、１，３－ビス（４－シアネートフェニル－１－（メチルエチリデン））ベンゼン、ビス（４－シアネートフェニル）チオエーテル、及びビス（４－シアネートフェニル）エーテル等の２官能シアネート樹脂、フェノールノボラック及びクレゾールノボラック等から誘導される多官能シアネート樹脂、これらシアネート樹脂が一部トリアジン化したプレポリマーなどが挙げられる。シアネートエステル系硬化剤の具体例としては、ロンザジャパン社製の「ＰＴ３０」及び「ＰＴ６０」（いずれもフェノールノボラック型多官能シアネートエステル樹脂）、「ＢＡ２３０」、「ＢＡ２３０Ｓ７５」（ビスフェノールＡジシアネートの一部又は全部がトリアジン化され三量体となったプレポリマー）等が挙げられる。 Examples of the cyanate ester-based curing agent include bisphenol A disicianate, polyphenol cyanate (oligo (3-methylene-1,5-phenylencyanate)), 4,4'-methylenebis (2,6-dimethylphenylcyanate), 4, 4'-Etilidendidiphenyl disianate, hexafluorobisphenol A disyanate, 2,2-bis (4-cyanate) phenylpropane, 1,1-bis (4-cyanate phenylmethane), bis (4-cyanate-3,5-) Bifunctional cyanate resins such as dimethylphenyl) methane, 1,3-bis (4-cyanatephenyl-1- (methylethylidene)) benzene, bis (4-cyanatephenyl) thioether, and bis (4-cyanatephenyl) ether, Examples thereof include polyfunctional cyanate resins derived from phenol novolac, cresol novolak and the like, and prepolymers in which these cyanate resins are partially triazined. Specific examples of the cyanate ester-based curing agent include "PT30" and "PT60" (both are phenol novolac type polyfunctional cyanate ester resins), "BA230", and "BA230S75" (part of bisphenol A disocyanate) manufactured by Lonza Japan. Alternatively, a prepolymer in which all of them are triazined to form a trimer) and the like can be mentioned.
　カルボジイミド系硬化剤の具体例としては、日清紡ケミカル社製の「Ｖ－０３」、「Ｖ－０７」等が挙げられる。 Specific examples of the carbodiimide-based curing agent include "V-03" and "V-07" manufactured by Nisshinbo Chemical Co., Ltd.
　イミダゾール系硬化剤としては、例えば、２－メチルイミダゾール、２－ウンデシルイミダゾール、２－ヘプタデシルイミダゾール、１，２－ジメチルイミダゾール、２－エチル－４－メチルイミダゾール、１，２－ジメチルイミダゾール、２－エチル－４－メチルイミダゾール、２－フェニルイミダゾール、２－フェニル－４－メチルイミダゾール、１－ベンジル－２－メチルイミダゾール、１－ベンジル－２－フェニルイミダゾール、１－シアノエチル－２－メチルイミダゾール、１－シアノエチル－２－ウンデシルイミダゾール、１－シアノエチル－２－エチル－４－メチルイミダゾール、１－シアノエチル－２－フェニルイミダゾール、１－シアノエチル－２－ウンデシルイミダゾリウムトリメリテイト、１－シアノエチル－２－フェニルイミダゾリウムトリメリテイト、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、２，４－ジアミノ－６－［２’－ウンデシルイミダゾリル－（１’）］－エチル－ｓ－トリアジン、２，４－ジアミノ－６－［２’－エチル－４’－メチルイミダゾリル－（１’）］－エチル－ｓ－トリアジン、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、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ル酸付加物、２－フェニルイミダゾールイソシアヌル酸付加物、２－フェニル－４，５－ジヒドロキシメチルイミダゾール、２－フェニル－４－メチル－５－ヒドロキシメチルイミダゾール、２，３－ジヒドロ－１Ｈ－ピロロ［１，２－ａ］ベンズイミダゾール、１－ドデシル－２－メチル－３－ベンジルイミダゾリウムクロライド、２－メチルイミダゾリン、２－フェニルイミダゾリン、等のイミダゾール化合物及びイミダゾール化合物とエポキシ樹脂とのアダクト体が挙げられる。 Examples of the imidazole-based curing agent include 2-methylimidazole, 2-undecyl imidazole, 2-heptadecyl imidazole, 1,2-dimethyl imidazole, 2-ethyl-4-methyl imidazole, 1,2-dimethyl imidazole, 2 -Ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1 -Cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimerite, 1-cyanoethyl-2 -Phenylimidazolium trimellitate, 2,4-diamino-6- [2'-methylimidazolyl- (1')]-ethyl-s-triazine, 2,4-diamino-6- [2'-undecylimidazolyl -(1')]-Ethyl-s-triazine, 2,4-diamino-6- [2'-ethyl-4'-methylimidazolyl- (1')]-ethyl-s-triazine, 2,4-diamino -6- [2'-methylimidazolyl- (1')] -ethyl-s-triazine, 2,4-diamino-6- [2'-methylimidazolyl- (1')]-ethyl-s-triazine isocyanuric acid Additives, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo [1, 2-a] Examples thereof include imidazole compounds such as benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline, 2-phenylimidazoline, and adducts of imidazole compounds and epoxy resins.
　イミダゾール系硬化剤としては、市販品を用いてもよく、例えば、三菱ケミカル社製の「Ｐ２００－Ｈ５０」等が挙げられる。 As the imidazole-based curing agent, a commercially available product may be used, and examples thereof include "P200-H50" manufactured by Mitsubishi Chemical Corporation.
　エポキシ樹脂とエポキシ樹脂硬化剤との量比は、［エポキシ樹脂のエポキシ基の合計数］：［エポキシ樹脂硬化剤の反応基の合計数］の比率で、１：０．２～１：２の範囲が好ましく、１：０．３～１：１．５がより好ましく、１：０．４～１：１．２がさらに好ましい。ここで、エポキシ樹脂硬化剤の反応基とは、活性水酸基、活性エステル基等であり、硬化剤の種類によって異なる。また、エポキシ樹脂のエポキシ基の合計数とは、各エポキシ樹脂の不揮発成分質量をエポキシ当量で除した値をすべてのエポキシ樹脂について合計した値であり、エポキシ樹脂硬化剤の反応基の合計数とは、各エポキシ樹脂硬化剤の不揮発成分質量を反応基当量で除した値をすべてのエポキシ樹脂硬化剤について合計した値である。エポキシ樹脂とエポキシ樹脂硬化剤との量比を斯かる範囲とすることにより、得られる磁性硬化物の耐熱性がより向上する。 The amount ratio of the epoxy resin to the epoxy resin curing agent is the ratio of [total number of epoxy groups in the epoxy resin]: [total number of reactive groups in the epoxy resin curing agent], which is 1: 0.2 to 1: 2. The range is preferable, 1: 0.3 to 1: 1.5 is more preferable, and 1: 0.4 to 1: 1.2 is even more preferable. Here, the reactive group of the epoxy resin curing agent is an active hydroxyl group, an active ester group, or the like, and differs depending on the type of the curing agent. The total number of epoxy groups in the epoxy resin is the total number of all epoxy resins obtained by dividing the mass of non-volatile components of each epoxy resin by the epoxy equivalent, and is the total number of reactive groups in the epoxy resin curing agent. Is the sum of the values obtained by dividing the non-volatile component mass of each epoxy resin curing agent by the reaction group equivalent for all epoxy resin curing agents. By setting the amount ratio of the epoxy resin and the epoxy resin curing agent within such a range, the heat resistance of the obtained magnetic cured product is further improved.
［硬化促進剤］
　硬化促進剤としては、例えば、アミン系硬化促進剤、イミダゾール系硬化促進剤、リン系硬化促進剤、グアニジン系硬化促進剤、金属系硬化促進剤等が挙げられる。硬化促進剤は、アミン系硬化促進剤、イミダゾール系硬化促進剤、及びグアニジン系硬化促進剤が好ましく、イミダゾール系硬化促進剤がより好ましい。硬化促進剤は１種単独で用いてもよく、２種以上を組み合わせて用いてもよい。硬化促進剤は一般的には硬化剤と併用して用いられる。 [Curing accelerator]
Examples of the curing accelerator include amine-based curing accelerators, imidazole-based curing accelerators, phosphorus-based curing accelerators, guanidine-based curing accelerators, and metal-based curing accelerators. As the curing accelerator, an amine-based curing accelerator, an imidazole-based curing accelerator, and a guanidine-based curing accelerator are preferable, and an imidazole-based curing accelerator is more preferable. The curing accelerator may be used alone or in combination of two or more. The curing accelerator is generally used in combination with the curing agent.
　アミン系硬化促進剤としては、例えば、トリエチルアミン、トリブチルアミン、４－ジメチルアミノピリジン（ＤＭＡＰ）、ベンジルジメチルアミン、２，４，６，－トリス（ジメチルアミノメチル）フェノール、１，８－ジアザビシクロ（５，４，０）－ウンデセン等が挙げられ、４－ジメチルアミノピリジン、１，８－ジアザビシクロ（５，４，０）－ウンデセン等の脂肪族アミン系硬化剤；ベンジジン、ｏ－トリジン、４，４’－ジアミノジフェニルメタン、４、４’－ジアミノ－３，３’－ジメチルジフェニルメタン（市販品としては日本化薬製の「カヤボンドＣ－１００」）、４、４’－ジアミノ－３，３’－ジエチルジフェニルメタン（市販品としては日本化薬製の「カヤハードＡ－Ａ」）、４、４’－ジアミノ－３，３’，５，５’－テトラメチルジフェニルメタン（市販品としては日本化薬製の「カヤボンドＣ－２００Ｓ」）、４、４’－ジアミノ－３，３’，５，５’－テトラエチルジフェニルメタン（市販品としては日本化薬製の「カヤボンドＣ－３００Ｓ」）、４、４’－ジアミノ－３，３’－ジエチル－５，５’－ジメチルジフェニルメタン、４，４’－ジアミノジフェニルエーテル、１，３－ビス（３－アミノフェノキシ）ベンゼン、１，３－ビス（４－アミノフェノキシ）ベンゼン、１，４－ビス（３－アミノフェノキシ）ベンゼン、１，４－ビス（４－アミノフェノキシ）ベンゼン、１，３－ビス（４－アミノフェノキシ）ネオペンタン、４，４’－［１，３－フェニレンビス（１－メチル－エチリデン）］ビスアニリン（市販品としては三井化学製の「ビスアニリンＭ」）、４，４’－［１，４－フェニレンビス（１－メチル－エチリデン）］ビスアニリン（市販品としては三井化学製の「ビスアニリンＰ」）、２，２－ビス［４－（４－アミノフェノキシ）フェニル］プロパン（市販品としては和歌山精化製の「ＢＡＰＰ」）、２，２－ビス［４－（４－アミノフェノキシ）フェニル］ヘキサフルオロプロパン、４，４’－ビス（４－アミノフェノキシ）ビフェニル等の芳香族アミン系硬化剤が挙げられる。 Examples of the amine-based curing accelerator include triethylamine, tributylamine, 4-dimethylaminopyridine (DMAP), benzyldimethylamine, 2,4,6, -tris (dimethylaminomethyl) phenol, and 1,8-diazabicyclo (5). , 4,0) -Undecene, etc., and aliphatic amine-based curing agents such as 4-dimethylaminopyridine, 1,8-diazabicyclo (5,4,5) -Undecene; benzidine, o-trizine, 4,4 '-Diaminodiphenylmethane, 4,4'-diamino-3,3'-dimethyldiphenylmethane (commercially available "Kayabond C-100" manufactured by Nippon Kayaku), 4,4'-diamino-3,3'-diethyl Diphenylmethane (commercially available "Kayahard AA" manufactured by Nippon Kayaku), 4,4'-diamino-3,3', 5,5'-tetramethyldiphenylmethane (commercially available "Kayahard AA" manufactured by Nippon Kayaku) Kayabond C-200S "), 4,4'-diamino-3,3', 5,5'-tetraethyldiphenylmethane ("Kayabond C-300S" manufactured by Nippon Kayaku Co., Ltd. as a commercial product), 4, 4'-diamino -3,3'-diethyl-5,5'-dimethyldiphenylmethane, 4,4'-diaminodiphenyl ether, 1,3-bis (3-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (3-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) neopentane, 4,4'-[1,3-phenylene Bis (1-methyl-ethylidene)] bisaniline (commercially available "bisaniline M" manufactured by Mitsui Chemicals, Inc.), 4,4'-[1,4-phenylenebis (1-methyl-ethylidene)] bisaniline (commercially available) Is Mitsui Chemicals' "Bisaniline P"), 2,2-bis [4- (4-aminophenoxy) phenyl] propane (commercially available "BAPP" made by Wakayama Seika), 2,2-bis [4 -(4-Aminophenoxy) phenyl] Hexafluoropropane, 4,4'-bis (4-aminophenoxy) biphenyl and other aromatic amine-based curing agents can be mentioned.
　イミダゾール系硬化促進剤としては、前記のイミダゾール系硬化剤で記載したものを挙げることができる。前記イミダゾール系硬化剤は、他の硬化剤と併用して用いる場合、硬化促進剤として機能する場合がある。 Examples of the imidazole-based curing accelerator include those described in the above-mentioned imidazole-based curing agent. When used in combination with other curing agents, the imidazole-based curing agent may function as a curing accelerator.
　イミダゾール系硬化促進剤としては、市販品を用いてもよく、前記のイミダゾール系硬化剤で記載したものを挙げることができる。 As the imidazole-based curing accelerator, a commercially available product may be used, and examples thereof include those described in the above-mentioned imidazole-based curing agent.
　リン系硬化促進剤としては、例えば、トリフェニルホスフィン、ホスホニウムボレート化合物、テトラフェニルホスホニウムテトラフェニルボレート、ｎ－ブチルホスホニウムテトラフェニルボレート、テトラブチルホスホニウムデカン酸塩、（４－メチルフェニル）トリフェニルホスホニウムチオシアネート、テトラフェニルホスホニウムチオシアネート、ブチルトリフェニルホスホニウムチオシアネート等が挙げられる。 Examples of the phosphorus-based curing accelerator include triphenylphosphine, phosphonium borate compound, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, and (4-methylphenyl) triphenylphosphonium thiocyanate. , Tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate and the like.
　グアニジン系硬化促進剤としては、例えば、ジシアンジアミド、１－メチルグアニジン、１－エチルグアニジン、１－シクロヘキシルグアニジン、１－フェニルグアニジン、１－（ｏ－トリル）グアニジン、ジメチルグアニジン、ジフェニルグアニジン、トリメチルグアニジン、テトラメチルグアニジン、ペンタメチルグアニジン、１，５，７－トリアザビシクロ［４．４．０］デカ－５－エン、７－メチル－１，５，７－トリアザビシクロ［４．４．０］デカ－５－エン、１－メチルビグアニド、１－エチルビグアニド、１－ｎ－ブチルビグアニド、１－ｎ－オクタデシルビグアニド、１，１－ジメチルビグアニド、１，１－ジエチルビグアニド、１－シクロヘキシルビグアニド、１－アリルビグアニド、１－フェニルビグアニド、１－（ｏ－トリル）ビグアニド等が挙げられる。 Examples of the guanidine-based curing accelerator include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1- (o-tolyl) guanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, and the like. Tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo [4.4.0] deca-5-ene, 7-methyl-1,5,7-triazabicyclo [4.4.0] Deca-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadesylbiguanide, 1,1-dimethylbiguanide, 1,1-diethylbiguanide, 1-cyclohexylbiguanide, 1 -Allyl biguanide, 1-phenylbiguanide, 1- (o-tolyl) biguanide and the like can be mentioned.
　金属系硬化促進剤としては、例えば、コバルト、銅、亜鉛、鉄、ニッケル、マンガン、スズ等の金属の、有機金属錯体又は有機金属塩が挙げられる。有機金属錯体の具体例としては、コバルト（ＩＩ）アセチルアセトナート、コバルト（ＩＩＩ）アセチルアセトナート等の有機コバルト錯体、銅（ＩＩ）アセチルアセトナート等の有機銅錯体、亜鉛（ＩＩ）アセチルアセトナート等の有機亜鉛錯体、鉄（ＩＩＩ）アセチルアセトナート等の有機鉄錯体、ニッケル（ＩＩ）アセチルアセトナート等の有機ニッケル錯体、マンガン（ＩＩ）アセチルアセトナート等の有機マンガン錯体等が挙げられる。有機金属塩としては、例えば、オクチル酸亜鉛、オクチル酸錫、ナフテン酸亜鉛、ナフテン酸コバルト、ステアリン酸スズ、ステアリン酸亜鉛等が挙げられる。 Examples of the metal-based curing accelerator include organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of the organic metal complex include an organic cobalt complex such as cobalt (II) acetylacetonate and cobalt (III) acetylacetonate, an organic copper complex such as copper (II) acetylacetonate, and zinc (II) acetylacetonate. Examples thereof include organic zinc complexes such as iron (III) acetylacetonate, organic nickel complexes such as nickel (II) acetylacetonate, and organic manganese complexes such as manganese (II) acetylacetonate. Examples of the organic metal salt include zinc octylate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, zinc stearate and the like.
　（Ｄ）硬化剤の含有量は、特に限定されるものではないが、樹脂組成物中の不揮発成分を１００質量％とした場合、好ましくは２５質量％以下、より好ましくは１５質量％以下、さらに好ましくは１０質量％以下である。その下限は、特に限定されるものではなく、例えば、０．０１質量％以上、０．１質量％以上、０．５質量％以上、１質量％以上等とし得る。 The content of the curing agent (D) is not particularly limited, but when the non-volatile component in the resin composition is 100% by mass, it is preferably 25% by mass or less, more preferably 15% by mass or less, and further. It is preferably 10% by mass or less. The lower limit is not particularly limited, and may be, for example, 0.01% by mass or more, 0.1% by mass or more, 0.5% by mass or more, 1% by mass or more, and the like.
＜（Ｅ）その他の添加剤＞
　樹脂組成物は、さらに必要に応じて、（Ｅ）その他の添加剤を含んでいてもよい。斯かるその他の添加剤としては、例えば、その他の樹脂成分、シランカップリング剤、非磁性無機充填材、分散剤、硬化遅延剤、難燃剤、増粘剤、消泡剤、レベリング剤、密着性付与剤、及び着色剤等の樹脂添加剤、有機溶剤等が挙げられる。その他の添加剤の含有量は、当業者により適宜設定され得る。 <(E) Other additives>
The resin composition may further contain (E) and other additives, if necessary. Such other additives include, for example, other resin components, silane coupling agents, non-magnetic inorganic fillers, dispersants, curing retardants, flame retardants, thickeners, defoamers, leveling agents, adhesions. Examples thereof include additives, resin additives such as colorants, and organic solvents. The content of other additives can be appropriately set by those skilled in the art.
＜樹脂組成物の特性＞
　本発明の樹脂組成物は、（Ｃ）脂環式エポキシ基を有するシロキサン化合物が配合されていることにより、（Ａ）磁性粉体と（Ｂ）エポキシ樹脂との界面電荷を非局在化させ、（Ａ）磁性粉体表面の抵抗値を向上させることができるため、本発明の樹脂組成物の磁性硬化物は、絶縁性に優れる。また、このような絶縁性は、一実施形態において、耐湿性に優れる。例えば、本発明の樹脂組成物を熱硬化して得られる磁性硬化物を、１３０℃、相対湿度８５％ＲＨにて、２００時間放置した後の当該磁性硬化物の抵抗値は、好ましくは１．０×１０６Ω以上、より好ましくは１．０×１０７Ω以上、さらに好ましくは１．０×１０８Ω以上、さらにより好ましくは１．０×１０９Ω以上、特に好ましくは１．０×１０１０Ω以上となり得る。 <Characteristics of resin composition>
The resin composition of the present invention contains (C) a siloxane compound having an alicyclic epoxy group to delocalize the interfacial charges between (A) the magnetic powder and (B) the epoxy resin. , (A) Since the resistance value on the surface of the magnetic powder can be improved, the magnetically cured product of the resin composition of the present invention has excellent insulating properties. In addition, such insulation is excellent in moisture resistance in one embodiment. For example, the resistance value of the magnetically cured product obtained by thermosetting the resin composition of the present invention after being left at 130 ° C. and a relative humidity of 85% RH for 200 hours is preferably 1. 0 × 10 6 Ω or more, more preferably 1.0 × 10 7 Ω or more, still more preferably 1.0 × 10 8 Ω or more, even more preferably 1.0 × 10 9 Ω or more, particularly preferably 1.0. × 10 Can be 10 Ω or more.
　本発明の樹脂組成物の磁性硬化物は、一実施形態において、優れた比透磁率を有する。例えば、本発明の樹脂組成物を熱硬化して得られる磁性硬化物の２３℃での比透磁率（μ’）は、好ましくは６．０以上、より好ましくは７．０以上、さらに好ましくは８．０以上、特に好ましくは８．５以上となり得る。 The magnetically cured product of the resin composition of the present invention has an excellent specific magnetic permeability in one embodiment. For example, the specific magnetic permeability (μ') of the magnetically cured product obtained by thermosetting the resin composition of the present invention at 23 ° C. is preferably 6.0 or more, more preferably 7.0 or more, and even more preferably 7.0 or more. It can be 8.0 or higher, particularly preferably 8.5 or higher.
＜樹脂組成物の製造方法＞
　樹脂組成物は、例えば、配合成分を、３本ロール、回転ミキサー、高速回転ミキサーなどの撹拌装置を用いて撹拌する方法によって製造できる。樹脂組成物は、製造後等に脱泡を行ってよい。例えば、静置による脱泡、遠心分離による脱泡、真空脱泡、撹拌脱泡、及びこれらの組合せ等による脱泡が挙げられる。 <Manufacturing method of resin composition>
The resin composition can be produced, for example, by a method of stirring the compounding components using a stirring device such as a three-roll, rotary mixer, or high-speed rotary mixer. The resin composition may be defoamed after production or the like. Examples thereof include defoaming by standing, defoaming by centrifugation, vacuum defoaming, stirring defoaming, and defoaming by a combination thereof.
　基板の磁性硬化物を形成するにあたって、樹脂組成物は、常温（２５℃）でペースト状の樹脂組成物（磁性ペースト）の形態で用いてもよく、該樹脂組成物の層を含む磁性シートの形態で用いてもよい。 In forming the magnetically cured product of the substrate, the resin composition may be used in the form of a paste-like resin composition (magnetic paste) at room temperature (25 ° C.), and the magnetic sheet containing the layer of the resin composition may be used. It may be used in a form.
［磁性ペースト］
　樹脂組成物は、液状のエポキシ樹脂等を使用することにより、有機溶剤を含まなくともペースト状の磁性ペーストとすることができる。磁性ペーストが有機溶媒を含む場合、その含有量は、磁性ペーストの全質量に対して、好ましくは１．０質量％未満、より好ましくは０．８質量％以下、さらに好ましくは０．５質量％以下、特に好ましくは０．１質量％以下である。下限は、特に制限はないが０．００１質量％以上、又は含有しないことである。磁性ペースト中の有機溶剤の含有量が少ない、または有機溶剤を含まないことにより、有機溶剤の揮発によるボイドの発生を抑制することができ、さらに取扱い性、作業性にも優れたものとすることができる。 [Magnetic paste]
By using a liquid epoxy resin or the like, the resin composition can be a paste-like magnetic paste even if it does not contain an organic solvent. When the magnetic paste contains an organic solvent, the content thereof is preferably less than 1.0% by mass, more preferably 0.8% by mass or less, still more preferably 0.5% by mass, based on the total mass of the magnetic paste. Hereinafter, it is particularly preferably 0.1% by mass or less. The lower limit is 0.001% by mass or more, or no content, without particular limitation. By having a small content of the organic solvent in the magnetic paste or not containing the organic solvent, it is possible to suppress the generation of voids due to the volatilization of the organic solvent, and the handleability and workability should be excellent. Can be done.
　磁性ペーストの粘度は、２５℃で好ましくは２０Ｐａ・ｓ以上、より好ましくは２５Ｐａ・ｓ以上、さらに好ましくは３０Ｐａ・ｓ以上、５０Ｐａ・ｓ以上であり、通常２００Ｐａ・ｓ未満、好ましくは１８０Ｐａ・ｓ以下、より好ましくは１６０Ｐａ・ｓ以下である。粘度は、磁性ペーストの温度を２５±２℃に保ち、Ｅ型粘度計を用いて測定することができる。 The viscosity of the magnetic paste is preferably 20 Pa · s or more, more preferably 25 Pa · s or more, further preferably 30 Pa · s or more, 50 Pa · s or more at 25 ° C., and usually less than 200 Pa · s, preferably 180 Pa · s. Hereinafter, it is more preferably 160 Pa · s or less. The viscosity can be measured using an E-type viscometer while keeping the temperature of the magnetic paste at 25 ± 2 ° C.
［磁性硬化物］
　本発明の樹脂組成物は、加熱することにより熱硬化させて磁性硬化物とすることができる。 [Magnetic cured product]
The resin composition of the present invention can be thermally cured by heating to obtain a magnetically cured product.
　磁性硬化物を得るための熱硬化条件は、樹脂組成物の組成や種類によっても異なるが、熱硬化温度は好ましくは１２０℃以上、より好ましくは１３０℃以上、さらに好ましくは１５０℃以上であり、好ましくは２４０℃以下、より好ましくは２２０℃以下、さらに好ましくは２００℃以下である。磁性硬化物を得るための熱硬化時間は、好ましくは５分以上、より好ましくは１０分以上、さらに好ましくは１５分以上であり、好ましくは１２０分以下、より好ましくは１００分以下、さらに好ましくは９０分以下である。 The thermosetting conditions for obtaining a magnetically cured product differ depending on the composition and type of the resin composition, but the thermosetting temperature is preferably 120 ° C. or higher, more preferably 130 ° C. or higher, still more preferably 150 ° C. or higher. It is preferably 240 ° C. or lower, more preferably 220 ° C. or lower, and even more preferably 200 ° C. or lower. The thermosetting time for obtaining the magnetically cured product is preferably 5 minutes or more, more preferably 10 minutes or more, still more preferably 15 minutes or more, preferably 120 minutes or less, more preferably 100 minutes or less, still more preferably. 90 minutes or less.
　樹脂組成物を熱硬化させる前に、樹脂組成物に対して、硬化温度よりも低い温度で加熱する予備加熱処理を施してもよい。予備加熱処理の温度は、好ましくは５０℃以上、好ましくは６０℃、より好ましくは７０℃以上、好ましくは１２０℃未満、好ましくは１１０℃以下、より好ましくは１００℃以である。予備加熱処理の時間は、通常好ましくは５分以上、より好ましくは１５分以上であり、好ましくは１５０分以下、より好ましくは１２０分以下である。 Before the resin composition is thermosetting, the resin composition may be subjected to a preheat treatment in which the resin composition is heated at a temperature lower than the curing temperature. The temperature of the preheat treatment is preferably 50 ° C. or higher, preferably 60 ° C. or higher, more preferably 70 ° C. or higher, preferably less than 120 ° C., preferably 110 ° C. or lower, and more preferably 100 ° C. or higher. The time of the preheat treatment is usually preferably 5 minutes or more, more preferably 15 minutes or more, preferably 150 minutes or less, and more preferably 120 minutes or less.
［磁性シート］
　磁性シートは、支持体と、該支持体上に設けられた、樹脂組成物で形成された樹脂組成物層とを含む。 [Magnetic sheet]
The magnetic sheet includes a support and a resin composition layer formed of the resin composition provided on the support.
　樹脂組成物層の厚さは、薄型化の観点から、好ましくは２５０μｍ以下、より好ましくは２００μｍ以下、さらに好ましくは１５０μｍ以下、１００μｍ以下である。樹脂組成物層の厚さの下限は、特に限定されないが、通常、５μｍ以上等とし得る。 The thickness of the resin composition layer is preferably 250 μm or less, more preferably 200 μm or less, still more preferably 150 μm or less, 100 μm or less from the viewpoint of thinning. The lower limit of the thickness of the resin composition layer is not particularly limited, but may be usually 5 μm or more.
　支持体としては、例えば、プラスチック材料からなるフィルム、金属箔、離型紙が挙げられ、プラスチック材料からなるフィルム、金属箔が好ましい。 Examples of the support include a film made of a plastic material, a metal foil, and a paper pattern, and a film made of a plastic material and a metal foil are preferable.
　支持体としてプラスチック材料からなるフィルムを使用する場合、プラスチック材料としては、例えば、ポリエチレンテレフタレート（以下「ＰＥＴ」と略称することがある。）、ポリエチレンナフタレート（以下「ＰＥＮ」と略称することがある。）等のポリエステル、ポリカーボネート（以下「ＰＣ」と略称することがある。）、ポリメチルメタクリレート（ＰＭＭＡ）等のアクリル、環状ポリオレフィン、トリアセチルセルロース（ＴＡＣ）、ポリエーテルサルファイド（ＰＥＳ）、ポリエーテルケトン、ポリイミド等が挙げられる。中でも、ポリエチレンテレフタレート、ポリエチレンナフタレートが好ましく、安価なポリエチレンテレフタレートが特に好ましい。 When a film made of a plastic material is used as the support, the plastic material may be, for example, polyethylene terephthalate (hereinafter abbreviated as "PET") or polyethylene naphthalate (hereinafter abbreviated as "PEN"). ) And other polyesters, polycarbonate (hereinafter sometimes abbreviated as "PC"), acrylics such as polymethylmethacrylate (PMMA), cyclic polyolefins, triacetylcellulose (TAC), polyethersulfide (PES), polyethers. Examples thereof include ketones and polyethylene. Of these, polyethylene terephthalate and polyethylene naphthalate are preferable, and inexpensive polyethylene terephthalate is particularly preferable.
　支持体として金属箔を使用する場合、金属箔としては、例えば、銅箔、アルミニウム箔等が挙げられ、銅箔が好ましい。銅箔としては、銅の単金属からなる箔を用いてもよく、銅と他の金属（例えば、スズ、クロム、銀、マグネシウム、ニッケル、ジルコニウム、ケイ素、チタン等）との合金からなる箔を用いてもよい。 When a metal foil is used as the support, examples of the metal foil include copper foil and aluminum foil, and copper foil is preferable. As the copper foil, a foil made of a single metal of copper may be used, and a foil made of an alloy of copper and another metal (for example, tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) may be used. You may use it.
　支持体は、樹脂組成物層と接合する面にマット処理、コロナ処理を施してあってもよい。 The support may be matted or corona-treated on the surface to be joined to the resin composition layer.
　また、支持体としては、樹脂組成物層と接合する面に離型層を有する離型層付き支持体を使用してもよい。離型層付き支持体の離型層に使用する離型剤としては、例えば、アルキド樹脂、ポリオレフィン樹脂、ウレタン樹脂、及びシリコーン樹脂からなる群から選択される１種以上の離型剤が挙げられる。離型層付き支持体は、市販品を用いてもよく、例えば、アルキド樹脂系離型剤を主成分とする離型層を有するＰＥＴフィルムである、リンテック社製の「ＳＫ－１」、「ＡＬ－５」、「ＡＬ－７」、東レ社製の「ルミラーＴ６０」、帝人社製の「ピューレックス」、ユニチカ社製の「ユニピール」等が挙げられる。 Further, as the support, a support with a release layer having a release layer on the surface to be joined with the resin composition layer may be used. Examples of the release agent used for the release layer of the support with the release layer include one or more release agents selected from the group consisting of alkyd resin, polyolefin resin, urethane resin, and silicone resin. .. As the support with a release layer, a commercially available product may be used. For example, "SK-1" and "SK-1" manufactured by Lintec Corporation, which are PET films having a release layer containing an alkyd resin-based release agent as a main component. Examples include "AL-5" and "AL-7", "Lumirror T60" manufactured by Toray Industries, Inc., "Purex" manufactured by Teijin Corporation, and "Unipee" manufactured by Unitika.
　支持体の厚みとしては、特に限定されないが、５μｍ～７５μｍの範囲が好ましく、１０μｍ～６０μｍの範囲がより好ましい。なお、離型層付き支持体を使用する場合、離型層付き支持体全体の厚さが上記範囲であることが好ましい。 The thickness of the support is not particularly limited, but is preferably in the range of 5 μm to 75 μm, and more preferably in the range of 10 μm to 60 μm. When a support with a release layer is used, the thickness of the entire support with a release layer is preferably in the above range.
　磁性シートは、例えば、有機溶剤に樹脂組成物を溶解した磁性ペーストを調製し、この磁性ペーストを、ダイコーター等を用いて支持体上に塗布し、更に乾燥させて樹脂組成物層を形成させることにより製造することができる。なお、樹脂組成物がペースト状の場合、ダイコーター等を用いて支持体上に直接樹脂組成物を塗布して樹脂組成物層を形成させることにより製造することができる。 For the magnetic sheet, for example, a magnetic paste in which a resin composition is dissolved in an organic solvent is prepared, and this magnetic paste is applied onto a support using a die coater or the like, and further dried to form a resin composition layer. It can be manufactured by. When the resin composition is in the form of a paste, it can be produced by directly applying the resin composition onto the support using a die coater or the like to form a resin composition layer.
　有機溶剤としては、例えば、アセトン、メチルエチルケトン（ＭＥＫ）及びシクロヘキサノン等のケトン類、酢酸エチル、酢酸ブチル、セロソルブアセテート、プロピレングリコールモノメチルエーテルアセテート及びカルビトールアセテート等の酢酸エステル類、セロソルブ及びブチルカルビトール等のカルビトール類、トルエン及びキシレン等の芳香族炭化水素類、ジメチルホルムアミド、ジメチルアセトアミド（ＤＭＡｃ）及びＮ－メチルピロリドン等のアミド系溶媒等を挙げることができる。有機溶剤は１種単独で使用してもよく、２種以上を組み合わせて使用してもよい。 Examples of the organic solvent include ketones such as acetone, methyl ethyl ketone (MEK) and cyclohexanone, acetic acid esters such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate and carbitol acetate, cellosolve and butyl carbitol and the like. Examples thereof include carbitols, aromatic hydrocarbons such as toluene and xylene, and amide solvents such as dimethylformamide, dimethylacetamide (DMAc) and N-methylpyrrolidone. The organic solvent may be used alone or in combination of two or more.
　乾燥は、加熱、熱風吹きつけ等の公知の方法により実施してよい。乾燥条件は特に限定されないが、樹脂組成物層中の有機溶剤の含有量が１０質量％以下、好ましくは５質量％以下となるように乾燥させる。磁性ペースト中の有機溶剤の沸点によっても異なるが、例えば３０質量％～６０質量％の有機溶剤を含む磁性ペーストを用いる場合、５０℃～１５０℃で３分間～１０分間乾燥させることにより、樹脂組成物層を形成することができる。 Drying may be carried out by a known method such as heating or blowing hot air. The drying conditions are not particularly limited, but the resin composition layer is dried so that the content of the organic solvent is 10% by mass or less, preferably 5% by mass or less. Although it depends on the boiling point of the organic solvent in the magnetic paste, for example, when a magnetic paste containing 30% by mass to 60% by mass of an organic solvent is used, the resin composition is obtained by drying at 50 ° C. to 150 ° C. for 3 to 10 minutes. A material layer can be formed.
　磁性シートにおいて、樹脂組成物層の支持体と接合していない面（即ち、支持体とは反対側の面）には、支持体に準じた保護フィルムをさらに積層することができる。保護フィルムの厚さは、特に限定されるものではないが、例えば、１μｍ～４０μｍである。保護フィルムを積層することにより、樹脂組成物層の表面へのゴミ等の付着やキズを抑制することができる。磁性シートは、ロール状に巻きとって保存することが可能である。磁性シートが保護フィルムを有する場合、保護フィルムを剥がすことによって使用可能となる。 In the magnetic sheet, a protective film similar to the support can be further laminated on the surface of the resin composition layer that is not bonded to the support (that is, the surface opposite to the support). The thickness of the protective film is not particularly limited, but is, for example, 1 μm to 40 μm. By laminating the protective film, it is possible to suppress the adhesion of dust and the like to the surface of the resin composition layer and scratches. The magnetic sheet can be rolled up and stored. When the magnetic sheet has a protective film, it can be used by peeling off the protective film.
［インダクタ基板］
　本発明のインダクタ基板は、本発明の樹脂組成物（磁性ペースト等）の硬化物である磁性層を含む。ここで、インダクタ基板には、基板の導体パターンによりコイルを形成し、インダクタを基板に設けたインダクタ基板だけでなく、インダクタを設けた基板をチップインダクタ等の部品として、回路基板等の基板に実装したインダクタ基板も包含される。図１は、本発明の一実施形態に係るインダクタ基板の模式的な平面図である。インダクタ基板１は、基板１１と、磁性層１２と、導体で形成された配線１３とを備え、配線１３は、磁性層１２に覆われるとともに、配線１３はコア部１４を中心として渦巻状に形成されている。また、コア部１４は、磁性層１２が埋め込まれている。 [Inductor board]
The inductor substrate of the present invention contains a magnetic layer which is a cured product of the resin composition (magnetic paste or the like) of the present invention. Here, on the inductor substrate, a coil is formed by the conductor pattern of the substrate, and not only the inductor substrate on which the inductor is provided on the substrate but also the substrate provided with the inductor is mounted on the substrate such as a circuit board as a component such as a chip inductor. The inductor substrate is also included. FIG. 1 is a schematic plan view of an inductor substrate according to an embodiment of the present invention. The inductor substrate 1 includes a substrate 11, a magnetic layer 12, and a wiring 13 formed of a conductor. The wiring 13 is covered with the magnetic layer 12, and the wiring 13 is formed in a spiral shape around the core portion 14. Has been done. Further, a magnetic layer 12 is embedded in the core portion 14.
　以下、インダクタ基板の製造方法を通してインダクタ基板及びその製造方法について説明する。 Hereinafter, the inductor substrate and the manufacturing method thereof will be described through the manufacturing method of the inductor substrate.
　インダクタ基板の製造方法は、
　（１）樹脂組成物を基板上に吐出させ、該樹脂組成物を熱硬化させ、第１の磁性層を形成する工程、
　（２）第１の磁性層上に配線を形成する工程、
　（３）第１の磁性層、コア部及び配線上に樹脂組成物を吐出し、該樹脂組成物を熱硬化させ、第２の磁性層を形成する工程、
を含む。ここで、磁性層１２は、第１及び第２の磁性層を含めたものである。 The manufacturing method of the inductor substrate is
(1) A step of discharging a resin composition onto a substrate, thermosetting the resin composition, and forming a first magnetic layer.
(2) Step of forming wiring on the first magnetic layer,
(3) A step of ejecting a resin composition onto a first magnetic layer, a core portion and wiring, and thermosetting the resin composition to form a second magnetic layer.
including. Here, the magnetic layer 12 includes the first and second magnetic layers.
＜工程（１）＞
　工程（１）は、樹脂組成物を基板上に吐出させ、該樹脂組成物を熱硬化させ、第１の磁性層を形成する。工程（１）を行うにあたって、樹脂組成物を準備する工程を含んでいてもよい。 <Process (1)>
In the step (1), the resin composition is discharged onto the substrate and the resin composition is thermosetting to form the first magnetic layer. In carrying out the step (1), a step of preparing the resin composition may be included.
　基板は、通常、絶縁性の基板である。基板の材料としては、例えば、ガラスエポキシ基板、金属基板、ポリエステル基板、ポリイミド基板、ＢＴレジン基板、熱硬化型ポリフェニレンエーテル基板等の絶縁性基材が挙げられる。基板は、その厚さ内に配線等が作り込まれた内層回路基板であってもよい。 The substrate is usually an insulating substrate. Examples of the substrate material include insulating substrates such as glass epoxy substrates, metal substrates, polyester substrates, polyimide substrates, BT resin substrates, and thermosetting polyphenylene ether substrates. The substrate may be an inner layer circuit board in which wiring or the like is built within the thickness thereof.
　樹脂組成物は、シリンジ、ニードル及びカートリッジ等に充填され、ディスペンサ等の吐出装置にて樹脂組成物を吐出することで基板上に塗布される。また、樹脂組成物は、全面印刷又はパターン印刷により、基板上に塗布されてもよい。塗布後に熱硬化され、第１の磁性層が得られる。 The resin composition is filled in a syringe, a needle, a cartridge, or the like, and is applied onto the substrate by discharging the resin composition with a discharge device such as a dispenser. Further, the resin composition may be applied onto the substrate by full-face printing or pattern printing. After coating, it is thermoset to obtain a first magnetic layer.
　樹脂組成物の熱硬化条件は、樹脂組成物の組成や種類によっても異なるが、硬化温度は好ましくは１２０℃以上、より好ましくは１３０℃以上、さらに好ましくは１５０℃以上であり、好ましくは２４０℃以下、より好ましくは２２０℃以下、さらに好ましくは２００℃以下である。樹脂組成物の硬化時間は、好ましくは５分以上、より好ましくは１０分以上、さらに好ましくは１５分以上であり、好ましくは１２０分以下、より好ましくは１００分以下、さらに好ましくは９０分以下である。 The thermosetting conditions of the resin composition differ depending on the composition and type of the resin composition, but the curing temperature is preferably 120 ° C. or higher, more preferably 130 ° C. or higher, still more preferably 150 ° C. or higher, preferably 240 ° C. or higher. Below, it is more preferably 220 ° C. or lower, still more preferably 200 ° C. or lower. The curing time of the resin composition is preferably 5 minutes or more, more preferably 10 minutes or more, further preferably 15 minutes or more, preferably 120 minutes or less, more preferably 100 minutes or less, still more preferably 90 minutes or less. is there.
　樹脂組成物を熱硬化させる前に、樹脂組成物に対して、硬化温度よりも低い温度で加熱する予備加熱処理を施してもよい。予備加熱処理の温度は、好ましくは５０℃以上、好ましくは６０℃、より好ましくは７０℃以上、好ましくは１２０℃未満、好ましくは１１０℃以下、より好ましくは１００℃以である。予備加熱処理の時間は、通常好ましくは５分以上、より好ましくは１５分以上であり、好ましくは１５０分以下、より好ましくは１２０分以下である。 Before the resin composition is thermosetting, the resin composition may be subjected to a preheat treatment in which the resin composition is heated at a temperature lower than the curing temperature. The temperature of the preheat treatment is preferably 50 ° C. or higher, preferably 60 ° C. or higher, more preferably 70 ° C. or higher, preferably less than 120 ° C., preferably 110 ° C. or lower, and more preferably 100 ° C. or higher. The time of the preheat treatment is usually preferably 5 minutes or more, more preferably 15 minutes or more, preferably 150 minutes or less, and more preferably 120 minutes or less.
＜工程（２）＞
　工程（２）では、工程（１）で形成した第１の磁性層上に配線を形成する。配線の形成方法は、例えば、めっき法、スパッタ法、蒸着法などが挙げられ、中でもめっき法が好ましい。好適な実施形態では、セミアディティブ法、フルアディティブ法等の適切な方法によって第１の磁性層の表面にめっきして、渦巻状の配線パターンを有する配線を形成する。 <Process (2)>
In the step (2), the wiring is formed on the first magnetic layer formed in the step (1). Examples of the wiring forming method include a plating method, a sputtering method, a vapor deposition method, and the like, and the plating method is particularly preferable. In a preferred embodiment, the surface of the first magnetic layer is plated by an appropriate method such as a semi-additive method or a full-additive method to form a wiring having a spiral wiring pattern.
　配線の材料としては、例えば、金、白金、パラジウム、銀、銅、アルミニウム、コバルト、クロム、亜鉛、ニッケル、チタン、タングステン、鉄、スズ、インジウム等の単金属；金、白金、パラジウム、銀、銅、アルミニウム、コバルト、クロム、亜鉛、ニッケル、チタン、タングステン、鉄、スズ及びインジウムの群から選択される２種以上の金属の合金が挙げられる。中でも、汎用性、コスト、パターニングの容易性等の観点から、クロム、ニッケル、チタン、アルミニウム、亜鉛、金、パラジウム、銀若しくは銅、又はニッケルクロム合金、銅ニッケル合金、銅チタン合金を用いることが好ましく、クロム、ニッケル、チタン、アルミニウム、亜鉛、金、パラジウム、銀若しくは銅、又はニッケルクロム合金を用いることがより好ましく、銅を用いることがさらに好ましい。 Wiring materials include, for example, single metals such as gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin and indium; gold, platinum, palladium, silver, Examples include alloys of two or more metals selected from the group of copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin and indium. Above all, from the viewpoint of versatility, cost, ease of patterning, etc., it is possible to use chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or nickel-chromium alloy, copper nickel alloy, copper titanium alloy. It is preferable to use chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or a nickel-chromium alloy, and it is even more preferable to use copper.
　ここで、第１の磁性層上に配線を形成する実施形態の例を、詳細に説明する。第１の磁性層の面に、無電解めっきにより、めっきシード層を形成する。次いで、形成されためっきシード層上に、電解めっきにより電解めっき層を形成し、必要に応じて、不要なめっきシード層をエッチング等の処理により除去して、所望の配線パターンを有する配線を形成できる。配線を形成後、配線のピール強度を向上させる等の目的で、必要によりアニール処理を行ってもよい。アニール処理は、例えば、基板を１５０～２００℃で２０～９０分間加熱することにより行うことができる。 Here, an example of an embodiment in which wiring is formed on the first magnetic layer will be described in detail. A plating seed layer is formed on the surface of the first magnetic layer by electroless plating. Next, an electrolytic plating layer is formed on the formed plating seed layer by electrolytic plating, and if necessary, an unnecessary plating seed layer is removed by a treatment such as etching to form a wiring having a desired wiring pattern. it can. After forming the wiring, annealing treatment may be performed if necessary for the purpose of improving the peel strength of the wiring. The annealing treatment can be performed, for example, by heating the substrate at 150 to 200 ° C. for 20 to 90 minutes.
　配線を形成後、形成されためっきシード層上に、渦巻状のパターンに対応して、めっきシード層の一部を露出させるマスクパターンを形成する。この場合、露出しためっきシード層上に、電解めっきにより電解めっき層を形成した後、マスクパターンを除去する。その後、不要なめっきシード層をエッチング等の処理により除去して、所望のパターンを有する配線を形成する。 After forming the wiring, a mask pattern is formed on the formed plating seed layer to expose a part of the plating seed layer corresponding to the spiral pattern. In this case, the mask pattern is removed after forming an electrolytic plating layer by electrolytic plating on the exposed plating seed layer. Then, the unnecessary plating seed layer is removed by a treatment such as etching to form a wiring having a desired pattern.
　配線の厚さは、薄型化の観点から、好ましくは７０μｍ以下であり、より好ましくは６０μｍ以下であり、さらに好ましくは５０μｍ以下、さらにより好ましくは４０μｍ以下、特に好ましくは３０μｍ以下、２０μｍ以下、１５μｍ以下又は１０μｍ以下である。下限は好ましくは１μｍ以上、より好ましくは３μｍ以上、さらに好ましくは５μｍ以上である。 The thickness of the wiring is preferably 70 μm or less, more preferably 60 μm or less, still more preferably 50 μm or less, still more preferably 40 μm or less, particularly preferably 30 μm or less, 20 μm or less, 15 μm from the viewpoint of thinning. It is less than or equal to 10 μm or less. The lower limit is preferably 1 μm or more, more preferably 3 μm or more, still more preferably 5 μm or more.
＜工程（３）＞
　工程（３）は、第１の磁性層、コア部及び配線上に樹脂組成物を吐出し、該樹脂組成物を熱硬化させ、第２の磁性層を形成する。第２の磁性層の形成方法は、第１の磁性層と同様である。第１の磁性層を形成する樹脂組成物と、第２の磁性層を形成する樹脂組成物とは、同一でも相異なっていてもよい。 <Process (3)>
In the step (3), the resin composition is discharged onto the first magnetic layer, the core portion and the wiring, and the resin composition is thermosetting to form the second magnetic layer. The method for forming the second magnetic layer is the same as that for the first magnetic layer. The resin composition forming the first magnetic layer and the resin composition forming the second magnetic layer may be the same or different from each other.
　工程（１）後、第１の磁性層上に絶縁層を形成する工程を設けてもよい。また、工程（２）後、配線上に絶縁層を形成する工程を設けてもよい。絶縁層は、回路基板の絶縁層と同様に形成してもよく、該回路基板の絶縁層と同様の材料を用いてもよい。 After the step (1), a step of forming an insulating layer on the first magnetic layer may be provided. Further, after the step (2), a step of forming an insulating layer on the wiring may be provided. The insulating layer may be formed in the same manner as the insulating layer of the circuit board, or the same material as the insulating layer of the circuit board may be used.
［回路基板］
　回路基板は、本発明のインダクタ基板を含む。回路基板は、半導体チップ等の電子部品を搭載するための基板として用いることができ、かかる回路基板を内層基板として使用した多層回路基板（多層プリント配線板）として用いることもできる。また、かかる回路基板を個片化したチップインダクタ部品として用いることもでき、該チップインダクタ部品を表面実装した回路基板として用いることもできる。 [Circuit board]
The circuit board includes the inductor board of the present invention. The circuit board can be used as a board for mounting electronic components such as semiconductor chips, and can also be used as a multi-layer circuit board (multi-layer printed wiring board) using such a circuit board as an inner layer board. Further, the circuit board can be used as an individualized chip inductor component, or the chip inductor component can be used as a surface-mounted circuit board.
　またかかる回路基板を用いて、種々の態様の半導体装置を製造することができる。かかる回路基板を含む半導体装置は、電気製品（例えば、コンピューター、携帯電話、デジタルカメラおよびテレビ等）および乗物（例えば、自動二輪車、自動車、電車、船舶および航空機等）等に好適に用いることができる。 Further, various types of semiconductor devices can be manufactured by using such a circuit board. The semiconductor device including such a circuit board can be suitably used for electric products (for example, computers, mobile phones, digital cameras, televisions, etc.) and vehicles (for example, motorcycles, automobiles, trains, ships, aircraft, etc.) and the like. ..
　以下、本発明を実施例により具体的に説明するが、本発明はこれらの実施例に限定されるものではない。なお、以下の記載において、「％」は、別途明示のない限り、「質量％」を意味する。 Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited to these Examples. In the following description, "%" means "mass%" unless otherwise specified.
＜実施例１＞
　磁性粉体（パウダーテック社製「Ｍ０５Ｓ」、Ｆｅ－Ｍｎ系フェライト粉末、Ｄ５０（メジアン径）：５μｍ）を８０質量部に対して、シロキサン化合物（「ＫＲ－４７０」、主成分：下記式（２）の化合物、信越化学社製）を５質量部、ビスフェノール型エポキシ樹脂（「ＺＸ－１０５９」、ビスフェノールＡ型エポキシ樹脂とビスフェノールＦ型エポキシ樹脂の混合品、新日鉄住金化学社製）を８質量部、グリシジルアミン型エポキシ樹脂（「ＥＰ－３９８０Ｓ」、グリシジルエーテル型含窒素芳香族エポキシ、ＡＤＥＫＡ製）を５質量部、イミダゾール系硬化剤（「２Ｐ４ＭＺ」、２－フェニル－４－メチルイミダゾール、四国化成社製）を２質量部加え、高速回転ミキサーで均一に分散し、樹脂組成物を調製した。 <Example 1>
80 parts by mass of magnetic powder (“M05S” manufactured by Powder Tech, Fe-Mn-based ferrite powder, D 50 (median diameter): 5 μm) with respect to 80 parts by mass of a siloxane compound (“KR-470”, main component: the following formula 5 parts by mass of the compound (2), manufactured by Shin-Etsu Chemical Co., Ltd., 8 parts of bisphenol type epoxy resin ("ZX-1059", a mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin, manufactured by Nippon Steel & Sumitomo Metal Corporation) By weight, 5 parts by weight of glycidylamine type epoxy resin ("EP-3980S", glycidyl ether type nitrogen-containing aromatic epoxy, manufactured by ADEKA), imidazole-based curing agent ("2P4MZ", 2-phenyl-4-methylimidazole, 2 parts by mass (manufactured by Shikoku Kasei Co., Ltd.) was added and uniformly dispersed with a high-speed rotary mixer to prepare a resin composition.
Figure JPOXMLDOC01-appb-C000004
Figure JPOXMLDOC01-appb-C000004
＜実施例２＞
　シロキサン化合物（「ＫＲ－４７０」、信越化学社製）５質量部の代わりに、シロキサン化合物（「Ｘ－４０－２６６７」、主成分：下記式（３）の化合物、信越化学社製）５質量部を使用した以外は、実施例１と同様にして、樹脂組成物を調製した。 <Example 2>
Instead of 5 parts by mass of siloxane compound ("KR-470", manufactured by Shin-Etsu Chemical Co., Ltd.), 5 parts by mass of siloxane compound ("X-40-2667", main component: compound of the following formula (3), manufactured by Shin-Etsu Chemical Co., Ltd.) A resin composition was prepared in the same manner as in Example 1 except that the parts were used.
Figure JPOXMLDOC01-appb-C000005
Figure JPOXMLDOC01-appb-C000005
＜実施例３＞
　シロキサン化合物（「ＫＲ－４７０」、信越化学社製）５質量部の代わりに、シロキサン化合物（「Ｘ－４０－２７１５」、主成分：下記式（４）の化合物、信越化学社製）５質量部を使用した以外は、実施例１と同様にして、樹脂組成物を調製した。 <Example 3>
Instead of 5 parts by mass of siloxane compound ("KR-470", manufactured by Shin-Etsu Chemical Co., Ltd.), 5 parts by mass of siloxane compound ("X-40-2715", main component: compound of the following formula (4), manufactured by Shin-Etsu Chemical Co., Ltd.) A resin composition was prepared in the same manner as in Example 1 except that the parts were used.
Figure JPOXMLDOC01-appb-C000006
Figure JPOXMLDOC01-appb-C000006
＜実施例４＞
　磁性粉体（パウダーテック社製「Ｍ０５Ｓ」、Ｆｅ－Ｍｎ系フェライト粉末、Ｄ５０（メジアン径）：５μｍ）８０質量部の代わりに、磁性粉体（パウダーテック社製「ＭＺ０５Ｓ」、Ｆｅ－Ｚｎ系フェライト粉末、Ｄ５０（メジアン径）：５μｍ）８０質量部を使用した以外は、実施例１と同様にして、樹脂組成物を調製した。 <Example 4>
Magnetic powder (Powder Tech "M05S", Fe-Mn-based ferrite powder, D 50 (median diameter): 5 μm) Instead of 80 parts by mass, magnetic powder (Powder Tech "MZ05S", Fe-Zn) A resin composition was prepared in the same manner as in Example 1 except that 80 parts by mass of the system ferrite powder, D 50 (median diameter): 5 μm) was used.
＜実施例５＞
　磁性粉体（パウダーテック社製「Ｍ０５Ｓ」、Ｆｅ－Ｍｎ系フェライト粉末、Ｄ５０（メジアン径）：５μｍ）８０質量部の代わりに、磁性粉体（エプソンアトミックス社製「ＰＦ－３Ｆ」、Ｆｅ－Ｓｉ系合金粉末、Ｄ５０（メジアン径）：３μｍ）８０質量部を使用した以外は、実施例１と同様にして、樹脂組成物を調製した。 <Example 5>
Magnetic powder ("M05S" manufactured by Powder Tech, Fe-Mn-based ferrite powder, D 50 (median diameter): 5 μm) Instead of 80 parts by mass, magnetic powder ("PF-3F" manufactured by Epson Atmix), Fe-Si-based alloy powder, D 50 (median diameter): 3 [mu] m) were used in place of the 80 parts by weight, in the same manner as in example 1 to prepare a resin composition.
＜比較例１＞
　シロキサン化合物（「ＫＲ－４７０」、信越化学社製）５質量部の代わりに、シロキサン化合物（「ＫＲ－２５１」、固形分２０％（トルエン溶液）、不揮発主成分：下記式（５）の化合物、信越化学社製）２５質量部を使用した以外は、実施例１と同様にして、樹脂組成物を調製した。 <Comparative example 1>
Instead of 5 parts by mass of siloxane compound ("KR-470", manufactured by Shin-Etsu Chemical Co., Ltd.), siloxane compound ("KR-251", solid content 20% (toluene solution), non-volatile main component: compound of the following formula (5) , Shin-Etsu Chemical Co., Ltd.) A resin composition was prepared in the same manner as in Example 1 except that 25 parts by mass was used.
Figure JPOXMLDOC01-appb-C000007
Figure JPOXMLDOC01-appb-C000007
＜比較例２＞
　シロキサン化合物（「ＫＲ－４７０」、信越化学社製）５質量部の代わりに、シロキサン化合物（「ＫＲ－２２０ＬＰ」、主成分：下記式（６）の化合物、信越化学社製）５質量部を使用した以外は、実施例１と同様にして、樹脂組成物を調製した。 <Comparative example 2>
Instead of 5 parts by mass of the siloxane compound ("KR-470", manufactured by Shin-Etsu Chemical Co., Ltd.), 5 parts by mass of the siloxane compound ("KR-220LP", main component: the compound of the following formula (6), manufactured by Shin-Etsu Chemical Co., Ltd.) was used. A resin composition was prepared in the same manner as in Example 1 except that it was used.
Figure JPOXMLDOC01-appb-C000008
Figure JPOXMLDOC01-appb-C000008
＜比較例３＞
　シロキサン化合物（「ＫＲ－４７０」、信越化学社製）５質量部の代わりに、シランカップリング剤（「ＫＢＥ－０４」、主成分：下記式（７）の化合物、信越化学社製）５質量部を使用した以外は、実施例１と同様にして、樹脂組成物を調製した。 <Comparative example 3>
Instead of 5 parts by mass of siloxane compound ("KR-470", manufactured by Shin-Etsu Chemical Co., Ltd.), 5 mass of silane coupling agent ("KBE-04", main component: compound of the following formula (7), manufactured by Shin-Etsu Chemical Co., Ltd.) A resin composition was prepared in the same manner as in Example 1 except that the portion was used.
Figure JPOXMLDOC01-appb-C000009
Figure JPOXMLDOC01-appb-C000009
＜比較例４＞
　シロキサン化合物（「ＫＲ－４７０」、信越化学社製）５質量部の代わりに、シランカップリング剤（「ＫＢＭ－３０３」、主成分：下記式（８）の化合物、信越化学社製）５質量部を使用した以外は、実施例１と同様にして、樹脂組成物を調製した。 <Comparative example 4>
Instead of 5 parts by mass of siloxane compound ("KR-470", manufactured by Shin-Etsu Chemical Co., Ltd.), 5 mass of silane coupling agent ("KBM-303", main component: compound of the following formula (8), manufactured by Shin-Etsu Chemical Co., Ltd.) A resin composition was prepared in the same manner as in Example 1 except that the portion was used.
Figure JPOXMLDOC01-appb-C000010
Figure JPOXMLDOC01-appb-C000010
＜比較例５＞
　シロキサン化合物（「ＫＲ－４７０」、信越化学社製）５質量部の代わりに、フュームドシリカ（「アエロジルＡ２００」、エアロジル社製）５質量部を使用した以外は、実施例１と同様にして、樹脂組成物を調製した。 <Comparative example 5>
The same as in Example 1 except that 5 parts by mass of fumed silica ("Aerosil A200", manufactured by Aerosil) was used instead of 5 parts by mass of the siloxane compound ("KR-470", manufactured by Shinetsu Chemical Co., Ltd.). , Resin composition was prepared.
＜試験例１：比透磁率の測定＞
　支持体として、シリコーン系離型剤処理を施したポリエチレンテレフタレート（ＰＥＴ）フィルム（リンテック社製「ＰＥＴ５０１０１０」、厚さ５０μｍ）を用意した。実施例及び比較例の各樹脂組成物を上記ＰＥＴフィルムの離型面上に、乾燥後のペースト層の厚みが１００μｍとなるよう、ドクターブレードにて均一に塗布し、磁性シートを得た。得られた磁性シートを１８０℃で９０分間加熱することによりペースト層を熱硬化し、支持体を剥離することによりシート状の磁性硬化物を得た。得られた磁性硬化物を、幅５ｍｍ、長さ１８ｍｍの試験片に切断し、評価サンプルとした。この評価サンプルを、アジレントテクノロジーズ（Ａｇｉｌｅｎｔ　Ｔｅｃｈｎｏｌｏｇｉｅｓ社製、「ＨＰ８３６２Ｂ」）を用いて、３ターンコイル法にて測定周波数を１００ＭＨｚとし、室温（２３℃）にて比透磁率（μ’）を測定した。 <Test Example 1: Measurement of relative magnetic permeability>
As a support, a polyethylene terephthalate (PET) film (“PET501010” manufactured by Lintec Corporation, thickness 50 μm) treated with a silicone-based release agent was prepared. Each of the resin compositions of Examples and Comparative Examples was uniformly applied on the release surface of the PET film with a doctor blade so that the thickness of the paste layer after drying was 100 μm to obtain a magnetic sheet. The obtained magnetic sheet was heated at 180 ° C. for 90 minutes to thermally cure the paste layer, and the support was peeled off to obtain a sheet-like magnetically cured product. The obtained magnetically cured product was cut into test pieces having a width of 5 mm and a length of 18 mm to prepare an evaluation sample. This evaluation sample was measured using Agilent Technologies (manufactured by Agilent Technologies, "HP8362B") at a measurement frequency of 100 MHz by a 3-turn coil method and a specific magnetic permeability (μ') at room temperature (23 ° C.). ..
＜試験例２：絶縁性試験＞
　支持体として、Ｌ／Ｓ＝５０μｍ／５０μｍのＴＡＢテープ（三井金属（株）製、「ＡＪ－Ｃ０００２－３０／４０」）を用意した。実施例及び比較例の各樹脂組成物を上記ＴＡＢテープ上に、乾燥後のペースト層の厚みが１００μｍとなるようドクターブレードにて均一に塗布し、サンプルを得た。得られたサンプルを１８０℃で９０分間加熱することにより樹脂組成物を熱硬化し、硬化サンプルを得た。つづけてＨＡＳＴ試験機（楠本化成（株）製、「ＥＴＡＣ　ＰＭ４２２」）に１３０℃、相対湿度８５％ＲＨの条件下、２００時間放置し、その後の抵抗値（ＨＡＳＴ抵抗値）（Ω）を測定した。 <Test Example 2: Insulation test>
As a support, a TAB tape having L / S = 50 μm / 50 μm (manufactured by Mitsui Mining & Smelting Co., Ltd., “AJ-C0002-30 / 40”) was prepared. The resin compositions of Examples and Comparative Examples were uniformly applied onto the TAB tape with a doctor blade so that the thickness of the paste layer after drying was 100 μm, and samples were obtained. The resin composition was thermoset by heating the obtained sample at 180 ° C. for 90 minutes to obtain a cured sample. Subsequently, the HAST tester (“ETAC PM422” manufactured by Kusumoto Kasei Co., Ltd.) was left at 130 ° C. and a relative humidity of 85% RH for 200 hours, and then the resistance value (HAST resistance value) (Ω) was measured. did.
　実施例及び比較例の樹脂組成物の不揮発成分及びその含有量、並びに試験例の測定結果を下記表１に示す。 Table 1 below shows the non-volatile components of the resin compositions of Examples and Comparative Examples, their contents, and the measurement results of Test Examples.
Figure JPOXMLDOC01-appb-T000011
Figure JPOXMLDOC01-appb-T000011
　実施例１～５より、（Ｃ）脂環式エポキシ基を有するシロキサン化合物を含有する樹脂組成物を用いることにより、優れた比透磁率と、ＨＡＳＴ後の優れた絶縁性を備える磁性硬化物が得られることがわかった。一方、比較例１～５より、樹脂組成物に（Ｃ）成分が含まれない場合、硬化物の比透磁率は高いものの、（Ｃ）成分を含有させた場合に比べてＨＡＳＴ後の絶縁性が劣ることが分かった。 From Examples 1 to 5, by using (C) a resin composition containing a siloxane compound having an alicyclic epoxy group, a magnetically cured product having excellent relative permeability and excellent insulating properties after HAST can be obtained. It turned out to be obtained. On the other hand, from Comparative Examples 1 to 5, when the resin composition does not contain the component (C), the specific magnetic permeability of the cured product is high, but the insulating property after HAST is higher than that in the case where the component (C) is contained. Turned out to be inferior.
　１　　　　インダクタ基板
　１１　　　基板
　１２　　　磁性層
　１３　　　配線層
　１４　　　コア部
  1 Inductor board 11 Board 12 Magnetic layer 13 Wiring layer 14 Core part

Claims (13)

  1. 　（Ａ）磁性粉体、（Ｂ）エポキシ樹脂、及び（Ｃ）脂環式エポキシ基を有するシロキサン化合物を含む樹脂組成物。 A resin composition containing (A) a magnetic powder, (B) an epoxy resin, and (C) a siloxane compound having an alicyclic epoxy group.
  2. 　（Ｃ）成分が、式（１）：
    Figure JPOXMLDOC01-appb-C000001
     〔式中、Ｒは、それぞれ独立して、置換又は無置換のアルキル基、置換又は無置換のアルケニル基、又は置換又は無置換のアリール基を示し、Ｘは、それぞれ独立して、置換又は無置換のアルキレン基を示し、Ｙは、それぞれ独立して、脂環式エポキシ基を示し、ｎは、１以上の整数を示し、Ｒ１及びＲ２は、それぞれ独立して、置換又は無置換のアルキル基、置換又は無置換のアルケニル基、又は置換又は無置換のアリール基を示すか、或いはＲ１及びＲ２が一緒になって１個の－Ｏ－を示して互いに結合し、環状シロキサンを形成する。〕
    で表される化合物である、請求項１に記載の樹脂組成物。     The component (C) is the formula (1):
    Figure JPOXMLDOC01-appb-C000001
     [In the formula, R independently represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a substituted or unsubstituted aryl group, and X is independently substituted or unsubstituted, respectively. Substituted alkylene groups, Y each independently represents an alicyclic epoxy group, n represents an integer greater than or equal to 1, and R 1 and R 2 are independently substituted or unsubstituted, respectively. An alkyl group, a substituted or unsubstituted alkenyl group, or a substituted or unsubstituted aryl group is shown, or R 1 and R 2 are combined to show one —O— and bonded to each other to form a cyclic siloxane. Form. ]
    The resin composition according to claim 1, which is a compound represented by.
  3. 　（Ａ）成分が、酸化鉄粉及び鉄合金系金属粉からなる群より選ばれる１種類以上を含む、請求項１又は２に記載の樹脂組成物。 The resin composition according to claim 1 or 2, wherein the component (A) contains at least one selected from the group consisting of iron oxide powder and iron alloy-based metal powder.
  4. 　（Ａ）成分の含有量が、樹脂組成物中の不揮発成分を１００質量％とした場合、６０質量％～９８質量％である、請求項１～３の何れか１項に記載の樹脂組成物。 The resin composition according to any one of claims 1 to 3, wherein the content of the component (A) is 60% by mass to 98% by mass when the non-volatile component in the resin composition is 100% by mass. ..
  5. 　（Ｂ）成分が、２５℃で液状のエポキシ樹脂を含む、請求項１～４の何れか１項に記載の樹脂組成物。 The resin composition according to any one of claims 1 to 4, wherein the component (B) contains an epoxy resin liquid at 25 ° C.
  6. 　さらに（Ｄ）硬化剤を含む、請求項１～５の何れか１項に記載の樹脂組成物。 The resin composition according to any one of claims 1 to 5, further comprising (D) a curing agent.
  7. 　（Ｄ）成分が、イミダゾール系硬化剤である、請求項６に記載の樹脂組成物。 The resin composition according to claim 6, wherein the component (D) is an imidazole-based curing agent.
  8. 　２５℃でペースト状である、請求項１～７の何れか１項に記載の樹脂組成物。 The resin composition according to any one of claims 1 to 7, which is in the form of a paste at 25 ° C.
  9. 　樹脂組成物の磁性硬化物を１３０℃、相対湿度８５％ＲＨにて２００時間放置した後の当該磁性硬化物の抵抗値が、１．０×１０６Ω以上である、請求項１～８の何れか１項に記載の樹脂組成物。 Magnetic cured product of the resin composition 130 ° C., the resistance value of the magnetic cured product was allowed to stand for 200 hours at a relative humidity of 85% RH is at 1.0 × 10 6 Ω or more, of claims 1 to 8, The resin composition according to any one of the following items.
  10. 　樹脂組成物の磁性硬化物の２３℃での比透磁率（μ’）が、６．０以上である、請求項１～９の何れか１項に記載の樹脂組成物。 The resin composition according to any one of claims 1 to 9, wherein the magnetically cured product of the resin composition has a specific magnetic permeability (μ') at 23 ° C. of 6.0 or more.
  11. 　支持体と、当該支持体上に設けられた請求項１～１０の何れか１項に記載の樹脂組成物で形成された樹脂組成物層とを含む、磁性シート。 A magnetic sheet containing a support and a resin composition layer formed on the support according to the resin composition according to any one of claims 1 to 10.
  12. 　請求項１～１０の何れか１項に記載の樹脂組成物の磁性硬化物。 A magnetically cured product of the resin composition according to any one of claims 1 to 10.
  13. 　請求項１２に記載の磁性硬化物を含むインダクタ基板。 An inductor substrate containing the magnetically cured product according to claim 12.
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06120016A (en) * 1992-10-01 1994-04-28 Sumitomo Metal Mining Co Ltd Bonded magnet composition and bonded magnet
JPH06349617A (en) * 1993-06-04 1994-12-22 Sumitomo Metal Mining Co Ltd Composition for bonded magnet and bonded magnet
JPH09162019A (en) * 1995-12-07 1997-06-20 Sumitomo Metal Mining Co Ltd Composition for resin coupled magnet and resin coupled magnet made thereof
JP2001213966A (en) * 2000-02-01 2001-08-07 Shin Etsu Chem Co Ltd Novel silicone compound and cosmetic prepared by using same

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5234727B2 (en) 2007-09-27 2013-07-10 学校法人東京女子医科大学 Method for producing temperature-responsive chromatographic carrier, chromatographic carrier obtained therefrom, and use thereof
JP2009155690A (en) 2007-12-26 2009-07-16 Denso Corp Magnetic powder and curable resin composition containing the same

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06120016A (en) * 1992-10-01 1994-04-28 Sumitomo Metal Mining Co Ltd Bonded magnet composition and bonded magnet
JPH06349617A (en) * 1993-06-04 1994-12-22 Sumitomo Metal Mining Co Ltd Composition for bonded magnet and bonded magnet
JPH09162019A (en) * 1995-12-07 1997-06-20 Sumitomo Metal Mining Co Ltd Composition for resin coupled magnet and resin coupled magnet made thereof
JP2001213966A (en) * 2000-02-01 2001-08-07 Shin Etsu Chem Co Ltd Novel silicone compound and cosmetic prepared by using same

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