JP5941640B2 - Composite magnetic material - Google Patents

Description

  The present invention is used for the purpose of absorbing electromagnetic wave noise generated from an electronic device, etc., suppressing emission to the outside and entry from the outside, or preventing malfunction due to interference between components inside the electronic device. The composite magnetic material has the flexibility to follow irregularities such as circuit boards, electronic components, flexible printed wiring boards, etc., and is a basic process for surface mounting technology of electronic components such as chip components to the substrate. The present invention relates to a composite magnetic material that can be used for reflow soldering.

  In recent years, due to higher functionality of electronic devices, the operating frequency of electronic components has been increased, the intensity of emitted noise electromagnetic waves has increased, and a wider range of frequency components has been included. There is an increasing demand for further downsizing and weight reduction in these electronic devices. With this demand, electronic components used tend to be downsized, thinned, and mounted with high density. There is a problem that noise electromagnetic waves radiated from electronic components, printed wiring, or wiring between modules are likely to be generated as electronic devices are increased in frequency and mounted in high density.

In general, a composite magnetic material is used as a measure for suppressing noise electromagnetic waves in various electronic devices.
Examples of the composite magnetic material include binder resin such as chlorinated polyethylene rubber, acrylic rubber, and ethylene acrylic rubber, and powder of soft magnetic metal such as Sendust (Fe-Si-Al alloy), Permalloy (Fe-Ni alloy), Fe An electromagnetic wave suppression sheet in which atomized powder such as a Cr alloy is dispersed and formed into a sheet shape is known (for example, Patent Document 1).
The ability of the composite magnetic body to suppress noise electromagnetic waves depends on its thickness, and various thicknesses of composite magnetic bodies are supplied depending on the application. For this reason, in the supply of the composite magnetic material, a composite magnetic material having an arbitrary thickness is manufactured and laminated according to the user's request in order to improve manufacturing efficiency. For example, like the electromagnetic wave suppression sheet of the invention of Patent Document 1, a composite magnetic body using a thermoplastic resin is stacked as necessary and hot pressed, so that an electromagnetic wave suppression sheet having a desired thickness can be obtained. Has been.

  By the way, reflow soldering is a basic process for surface mounting technology of electronic parts such as chip parts to a substrate. General composite magnetic materials have poor heat resistance, so they are softened by heating in a reflow oven during reflow soldering and cannot retain their shape, or are in the form of local powdering, cracking, cracking, foaming, etc. Defects are likely to occur and cannot be used in high-temperature atmospheres such as reflow soldering. Therefore, the composite magnetic body has to be pasted after reflow soldering, which has been a process problem.

Conventionally, inventions that improve heat resistance and flexibility have been proposed.
For example, an electromagnetic wave suppression sheet in which flat soft magnetic powder is dispersed in a polyurethane resin is mounted on the upper surface of a semiconductor component, and heat such as a phenol resin, an epoxy resin, or an unsaturated polyester resin is covered so as to cover the electromagnetic wave suppression sheet. An invention has been proposed in which a curable resin is applied and fixed, and then passed through a solder reflow oven at 240 ° C. to cure the thermosetting resin, and the electromagnetic wave suppression sheet is sealed and fixed with the thermosetting resin (for example, Patent Document 2). According to the invention of Patent Document 2, it is described that the electromagnetic wave suppression sheet was not altered or malfunctioned even after the reflow process.
In addition, an electromagnetic wave suppression sheet in which soft magnetic metal powder is embedded in a thermosetting resin sheet of any one of an epoxy resin, an unsaturated polyester resin, a phenol resin, a melamine resin, and a urea resin has been proposed (for example, Patent Document 3). ).

Alternatively, an electromagnetic wave absorbing material composition comprising a compound having two or more carboxyl groups and / or acid anhydride groups in one molecule, a compound having two or more epoxy groups in one molecule, and soft magnetic powder Has been proposed (for example, Patent Document 4).
Further, for example, flat soft magnetic material powder, epoxy resin, epoxy resin curing agent, curing accelerator, epoxy group-containing acrylic copolymer containing glycidyl (meth) acrylate, dispersant, organic phosphinate compound, A flame retardant noise suppression sheet containing a metal hydroxide has been proposed (for example, Patent Document 5).

JP 2002-299112 A JP 11-307983 A JP 2002-111276 A JP 2005-252221 A JP 2009-59752 A

However, the inventions of Patent Documents 2 to 3 are not satisfactory in flexibility, although prevention of form defects (reflow resistance) is achieved in reflow soldering. Although the inventions of Patent Documents 4 to 5 are improved in flexibility, they are not satisfactory reflow resistance. In addition, since the composite magnetic body using a thermosetting resin is in a cured state, it is necessary to manufacture an electromagnetic wave suppression sheet according to the thickness of the final product in order to obtain an electromagnetic wave suppression sheet with a desired thickness. There was a problem that it was not possible to manufacture efficiently.
Accordingly, the present invention is directed to a composite magnetic body that can be efficiently manufactured and that can achieve both sufficient flexibility and reflow resistance.

In general, when engineering plastics with high heat resistance increase the amount of soft magnetic metal powder in order to obtain an electromagnetic wave suppression function, the molded body becomes brittle or the flexibility is impaired, so that a satisfactory composite magnetic body can be obtained. Is difficult. On the other hand, some thermoplastic resins having low heat resistance can increase the filling amount of the soft magnetic metal powder, but the heat resistance of the resulting composite magnetic material is insufficient.
As a result of intensive studies, the present inventors have blended a specific acrylonitrile-butadiene copolymer, a phenol resin, and a compound containing two or more maleimide groups at a specific ratio, thereby providing an electromagnetic wave suppressing function. The magnetic material can be sufficiently soft and reflow-resistant without damaging, and a soft magnetic metal powder is dispersed in a liquid resin composition to form a solution (A stage) magnetic coating. The coating material is applied to the base material and dried to obtain a semi-cured sheet material in a semi-cured state (B stage), and the semi-cured sheet material is cured to a cured state (C stage). Has been found that it is possible to efficiently produce a composite magnetic body having an arbitrary thickness by laminating as necessary and applying a heat press and laminating, resulting in the present invention.

That is, the composite magnetic body of the present invention comprises (A) component: an acrylonitrile-butadiene copolymer having a carboxyl group , (B) component: a phenol resin, and (C) component: a maleimide group represented by the following formula. A soft magnetic metal powder is dispersed in a resin composition containing two or more compounds (1) and (2).

前記軟磁性金属粉末は、軟磁性の金属または合金からなるアトマイズ粉末を扁平にした平均粒径３０〜２００μｍ、扁平度３０〜２００のフレーク状粉末であることが好ましく、Ｆｅ−Ｓｉ系合金粉末、Ｆｅ−Ｓｉ−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−Ｃｒ系合金粉末から選ばれる少なくとも１種であることがさらに好ましい。
前記軟磁性金属粉末／［（Ａ）成分＋（Ｂ）成分＋（Ｃ）成分］で表される質量比は、２〜１９であることが好ましい。

The soft magnetic metal powder is preferably a flaky powder having an average particle size of 30 to 200 μm and a flatness of 30 to 200 obtained by flattening an atomized powder made of a soft magnetic metal or alloy, Fe—Si alloy powder, It is at least one selected from Fe-Si-Al alloy powder, Fe-Ni alloy powder, Fe-Ni-Mo alloy powder, Fe-Ni-Mo-Cu alloy powder, and Fe-Cr alloy powder. More preferably.
The mass ratio represented by the soft magnetic metal powder / [(A) component + (B) component + (C) component] is preferably 2-19.

The component (A) is preferably an acrylonitrile-butadiene copolymer of 5-50% by mass of acrylonitrile, and the acrylonitrile-butadiene copolymer preferably has a Mooney viscosity of 50-90M _{1 + 4} (100 ° C.). preferable.
The component (B) is preferably a phenol resin containing a resol type alkylphenol, and more preferably a resol type phenol and a novolac type phenol are used in combination.
The component (C) preferably has a mass ratio of 1 to 15 represented by compound (2) / compound (1).
The mass ratio represented by (A) component / [(B) component + (C) component] is 0.1 to 10, and (B) component / [(B) component + (C) component]. Is preferably 0.1 to 0.9.

  In addition to the component (A), the component (B), and the component (C), the component (D) preferably contains a diamine compound, and the component (D) is a compound (3) represented by the following formula. The compound (4) represented by the following formula having a weight average molecular weight of 200 to 7,000 is more preferable.

（式中、Ｒ^１は２価の芳香族基を表す）

(Wherein R ¹ represents a divalent aromatic group)

（式中、Ｒ^２はプロピレン基またはフェノキシメチレン基を表し、ｎは０ないし７の整数を示す）

(Wherein R ² represents a propylene group or a phenoxymethylene group, and n represents an integer of 0 to 7)

The composite magnetic material of the present invention is selected from a flame retardant comprising aluminum hydroxide and / or magnesium hydroxide having an average particle size of 0.1 to 3 μm, red phosphorus, ammonium polyphosphate, melamine polyphosphate, and phosphate ester. It is preferable to contain at least one flame retardant aid, and the mass ratio represented by the flame retardant / [(A) component + (B) component + (C) component] is 0.4 to More preferably, the mass ratio represented by the flame retardant aid / [(A) component + (B) component + (C) component] is 0.01 to 0.1.
The composite magnetic body of the present invention preferably has a heat-resistant adhesive layer laminated on one side or both sides.

  According to the composite magnetic body of the present invention, an electromagnetic wave suppression sheet can be efficiently produced, and both sufficient flexibility and reflow resistance can be achieved.

(Composite magnetic material)
The composite magnetic body of the present invention is one in which soft magnetic metal powder is dispersed in a resin composition, for example, formed into a sheet shape.

<Resin composition>
The resin composition of the present invention contains (A) component: acrylonitrile-butadiene copolymer, (B) component: phenol resin, and (C) component: two or more maleimide groups represented by the following formula. It contains compound (1) and compound (2).

  2-50 mass% is preferable, as for content of the resin composition in a composite magnetic body, 5-40 mass% is more preferable, and 5-20 mass% is further more preferable. If it is less than the lower limit, the function of the soft magnetic metal powder as a binder may be impaired, and the moldability of the composite magnetic body may be impaired. If the upper limit is exceeded, the electromagnetic wave control performance of the composite magnetic body May be insufficient.

<(A) component: acrylonitrile-butadiene copolymer>
As the acrylonitrile-butadiene copolymer, all known acrylonitrile-butadiene copolymers can be used, but the content of acrylonitrile-derived monomer units in the acrylonitrile-butadiene copolymer (hereinafter referred to as AN content) is 5 to 50% by mass. Is preferable, 10-40 mass% is more preferable, and 10-30 mass% is further more preferable. When the AN content is less than the lower limit, it is difficult to improve the reflow resistance. When the AN content exceeds the upper limit, the solubility in a solvent is reduced or it is difficult to stack semi-cured sheets. The manufacturing workability of the composite magnetic body may be reduced.

As the acrylonitrile-butadiene copolymer, those having a carboxyl group are particularly preferred. Since the acrylonitrile-butadiene copolymer having a carboxyl group has a high melt viscosity at the time of heating, the thermal stability of the composite magnetic body can be increased, and the tensile strength of the composite magnetic body can be increased. In addition, since the acrylonitrile-butadiene copolymer having a carboxyl group is highly compatible with other resins, it is easy to increase the production efficiency or obtain a stable quality composite magnetic body.
The carboxyl group equivalent (value calculated from the number average molecular weight) in the acrylonitrile-butadiene copolymer having a carboxyl group is preferably 1000 to 20000.
Acrylonitrile having a carboxyl group - Mooney viscosity butadiene _{copolymer, 50~90M 1 + 4 (100 ℃} ) are _{preferred, 55~90M 1 + 4 (100 ℃} ) is more _{preferable, 60~70M 1 + 4 (100 ℃} ) is more preferred. When the Mooney viscosity is within the above range, the thermal stability of the composite magnetic material is improved, and the reflow resistance is further improved. In addition, when the Mooney viscosity is within the above range, the workability and adhesiveness of the magnetic coating material are improved due to the improvement in solvent solubility and the decrease in melt viscosity.

  When the Mooney viscosity is less than the above lower limit, the heat resistance of the resin composition is lowered, and the reflow resistance may be lowered. In addition, the melt viscosity of the semi-cured sheet decreases, and the flow of the magnetic coating material increases in the film forming process described later, which may reduce the workability. If the Mooney viscosity exceeds the above upper limit, the solubility in a solvent is reduced in the coating preparation process described later, or the fluidity of the magnetic coating material is decreased in the film forming process described later, making film formation difficult. Or it may become difficult to laminate semi-cured sheets, and the production efficiency of the composite magnetic body may be reduced. The Mooney viscosity is a value measured using a Mooney viscometer (manufactured by Shimadzu Corporation) in accordance with JIS K6300-1.

<(B) component: phenol resin>
As the phenol resin, known resins can be used, but the temperature when the semi-cured sheet material is stacked and laminated by applying a heat press, the temperature when the semi-cured sheet material is cured is low. In addition, a resol-type alkylphenol resin is preferable because a sufficient adhesion between semi-cured sheets can be obtained, and it is more preferable to use a resol-type phenol resin and a novolac-type phenol resin in combination. preferable. The mass ratio represented by resol type phenol resin / novolak type phenol resin is preferably 1 to 20, and more preferably 2 to 10. When the mass ratio is less than the above lower limit value, the novolak type phenolic resin is inferior in curability by itself, so that the curability is lowered and it is difficult to improve the reflow resistance. The tackiness is expressed on the surface of the sheet-like sheet material and is cheaper, and the workability when superimposing the semi-cured sheet material is lowered. Examples of the phenolic resin containing a resol type alkylphenol include pt-butylphenol resol resin. Examples of the novolak type phenolic resin include pt-butylphenol novolak resin, phenol novolac resin, cresol novolac resin, and bisphenol novolac resin. And poly p-vinylphenol novolac resin.

<(C) component: a compound containing two or more maleimide groups>
The compound containing two or more maleimide groups requires the combined use of the compound (1) and the compound (2) represented by the above formula, and the mass ratio represented by the compound (2) / compound (1) is 1 to 15 is preferable, and 1.3 to 6.5 is more preferable. When the mass ratio is less than the above lower limit, the temperature when the semi-cured sheet material is laminated, subjected to hot pressing and laminated, and the temperature when the semi-cured sheet material is in a cured state becomes high temperature, If the energy efficiency is deteriorated and the value exceeds the upper limit, it is difficult to improve the reflow resistance.

<(D) component: diamine compound>
The resin composition preferably contains a component (D): a diamine compound as a curing agent for the component (C) in order to adjust the curing temperature. The component (D) is a compound represented by the following formula (3 Or a compound (4).

（式中、Ｒ^１は２価の芳香族基を表す）

(Wherein R ¹ represents a divalent aromatic group)

（式中、Ｒ^２はプロピレン基またはフェノキシメチレン基を表し、ｎは０ないし７の整数
を示す）

(Wherein R ² represents a propylene group or a phenoxymethylene group, and n represents an integer of 0 to 7)

  The compound (3) is not particularly limited, and for example, 3,3′-diaminobiphenyl, 3,4′-diaminobiphenyl, 4,4′-diaminobiphenyl, 3,3′-diaminodiphenylmethane, 3,4 ′ -Diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 2,2- (3,3'-diaminodiphenyl) propane, 2,2- (3,4'-diaminodiphenyl) propane, 2,2- (4,4 '-Diaminodiphenyl) propane, 2,2- (3,3'-diaminodiphenyl) hexafluoropropane, 2,2- (3,4'-diaminodiphenyl) hexafluoropropane, 2,2- (4,4' -Diaminodiphenyl) hexafluoropropane, 3,3'-oxydianiline, 3,4'-oxydianiline, 4,4'-oxydianiline 3,3′-diaminodiphenylsulfide, 3,4′-diaminodiphenylsulfide, 4,4′-diaminodiphenylsulfide, 3,3′-diaminodiphenylsulfone, 3,4′-diaminodiphenylsulfone, 4,4 ′ -Diaminodiphenylsulfone, 1,3-bis [1- (3-aminophenyl) -1-methylethyl] benzene, 1,3-bis [1- (4-aminophenyl) -1-methylethyl] benzene, 1 , 4-bis [1- (3-aminophenyl) benzene, 1,3-bis (3-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (3-amino Phenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 3,3′-bis (3-aminophenoxy) diphenylate 3,3′-bis (4-aminophenoxy) diphenyl ether, 3,4′-bis (3-aminophenoxy) diphenyl ether, 3,4′-bis (4-aminophenoxy) diphenyl ether, 4,4′-bis ( 3-aminophenoxy) diphenyl ether, 4,4′-bis (4-aminophenoxy) diphenyl ether, 1,4-bis [1- (4-aminophenyl) -1-methylethyl-bis (3-aminophenoxy) biphenyl, 3,3′-bis (4-aminophenoxy) biphenyl, 3,4′-bis (3-aminophenoxy) biphenyl, 3,4′-bis (4-aminophenoxy) biphenyl, 4,4′-bis (3 -Aminophenoxy) biphenyl, 4,4'-bis (4-aminophenoxy) biphenyl, bis [4- (3-aminophen Enoxy) phenyl] sulfone, bis [4- (4-aminophenoxy) phenyl] sulfone, 2,2-bis [3- (3-aminophenoxy) phenyl] propane, 2,2-bis [3- (4-amino) Phenoxy) phenyl] propane, 2,2-bis [4- (3-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [3- (3-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis [3- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis [4- (3-aminophenoxy) phenyl] hexafluoro Propane, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 9,9-bis (3-aminopheny ) Fluorene, 9,9-bis (4-aminophenyl) fluorene, and the like.

Since the compound (4) is easily dissolved in a solvent and easy to handle, the weight average molecular weight is preferably 200 to 7,000.
The compound (4) is not particularly limited. For example, bis (3-aminopropyl) tetramethyldisiloxane, aminopropyl-terminated dimethylsiloxane tetramer, aminopropyl-terminated dimethylsiloxane octamer, bis (3- Aminophenoxymethyl) tetramethyldisiloxane and the like, and a mixture thereof may be used.

  The content of the component (D) is preferably 0.01 to 2.0 molar equivalents of the amino group of the component (D) with respect to 1 molar equivalent of the maleimide group of the component (C). More preferably, it is 1.0 molar equivalent. (D) When content of a component is less than the said lower limit, the temperature in the case of making a semi-cured sheet material into a hardening state, and the temperature in the case of laminating | stacking a semi-cured sheet material and giving a hot press, and laminating | stacking it. It becomes difficult to adjust the temperature, and if it exceeds the upper limit, it is difficult to improve the reflow resistance.

<Combination ratio>
As for the compounding ratio of the resin composition, the mass ratio represented by (A) component / [(B) component + (C) component] is preferably 0.1 to 10, and preferably 0.125 to 5. More preferably, it is more preferably 0.25-2. If the mass ratio is less than the lower limit, the flexibility of the semi-cured sheet is likely to be impaired, and if it exceeds the upper limit, it is difficult to improve reflow resistance.
At this time, the blend ratio of the (B) component and the (C) component is such that the mass ratio represented by (B) component / [(B) component + (C) component] is 0.1 to 0.9. It is preferable. If the mass ratio is less than the lower limit, the flexibility of the semi-cured sheet is likely to be impaired, and if it exceeds the upper limit, it is difficult to improve reflow resistance.

<Optional components in resin composition>
The resin composition may be diazabicyclooctane or methyl ethyl ketone peroxide, cyclohexane peroxide, 3, 3, 5 in order to promote the addition reaction between the components (A) and (B) as necessary. -Trimethylcyclohexanone peroxide, methylcyclohexanone peroxide, methyl acetoacetate peroxide, acetylacetone peroxide, 1,1-bis (t-butylperoxy) -3,3,5 trimethylhexane, 1,1-bis (t- Butylperoxy) -cyclohexane, 2,2-bis (t-butylperoxy) octane, n-butyl-4,4-bis (t-butylperoxy) valate, 2,2-bis (t-butylperoxy) ) Butane, t-butyl hydroperoxide, cumene hydride Peroxide, di-isopropylbenzene hydroperoxide, p-menthane hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, di -T-butyl peroxide, t-butyl cumyl peroxide, di-cumyl peroxide, α, α'-bis (t-butylperoxy-m-isopropyl) benzene, 2,5-dimethyl-2,5-di (T-butylperoxy) hexane, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne, acetyl peroxide, isobutyl peroxide, octanoyl peroxide, decanoyl peroxide, benzoyl peroxide , Lauroyl peroxide, 3,5,5-tri Methylhexanoyl peroxide, succinic acid peroxide, 2,4-dichlorobenzoyl peroxide, m-toluoyl peroxide, di-isopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, di-n- Propyl peroxydicarbonate, bis- (4-t-butylcyclohexyl) peroxydicarbonate, di-myristyl peroxydicarbonate, di-2-ethoxyethyl peroxydicarbonate, di-methoxyisopropyl peroxydicarbonate, Di (3-methyl-3-methoxybutyl) peroxydicarbonate, di-allyl peroxydicarbonate, t-butyl peroxyacetate, t-butyl peroxyisobutyrate, t-butyl peroxypi Rate, t-butylperoxyneodecanate, cumylperoxyneodecanate, t-butylperoxy-2-ethylhexanate, t-butylperoxy-3,5,5-trimethylhexanate, t-butylper Oxylaurate, t-butylperoxybenzoate, di-t-butylperoxyisophthalate, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, t-butylperoxymaleic acid, t-butyl Peroxyisopropyl carbonate, cumyl peroxyoctate, t-hexylperoxyneodecanate, t-hexylperoxypivalate, t-butylperoxyneohexanate, acetylcyclohexylsulfonyl peroxide, t-butylperoxyallylcarbonate Organic peracid such as 1,2-dimethylimidazole, 1-methyl-2-ethylimidazole, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 1 -Benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-benzyl-2-phenylimidazole trimellitic acid salt, 1-benzyl-2-ethylimidazole, 1-benzyl-2-ethyl-5- Methylimidazole, 2-ethylimidazole, 2-isopropylimidazole, 2-phenyl-4-benzylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2- Undecyl Imida Sol, 1-cyanoethyl-2-isopropylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2,4- Diamino-6- [2′-methylimidazolyl- (1 ′)]-ethyl-s-triazine, 2,4-diamino-6- [2′-ethyl-4-methylimidazolyl- (1 ′)]-ethyl- s-triazine, 2,4-diamino-6- [2'-undecylimidazolyl- (1 ')]-ethyl-s-triazine, 2-methylimidazolium isocyanuric acid adduct, 2-phenylimidazolium isocyanur Acid adduct, 2,4-diamino-6- [2'-methylimidazolyl- (1 ')]-ethyl-s-triazine- Sosocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-benzyl-5-hydroxymethylimidazole, 4,4′-methylene-bis- (2-ethyl-5-methylimidazole) 1-aminoethyl-2-methylimidazole, 1-cyanoethyl-2-phenyl-4,5-di (cyanoethoxymethyl) imidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazole Benzotriazole adduct, 1-aminoethyl-2-ethylimidazole, 1- (cyanoethylaminoethyl) -2-methylimidazole, N, N ′-[2-methylimidazolyl- (1) -ethyl] -adipoyl Diamide, N, N′-bis- (2-methylimidazolyl-1-ethyl) urine N, (2-methylimidazolyl-1-ethyl) urea, N, N ′-[2-methylimidazolyl- (1) -ethyl] dodecandioyldiamide, N, N ′-[2-methylimidazolyl- ( 1) -Ethyl] eicosanedioyl diamide, imidazoles such as 1-benzyl-2-phenylimidazole / hydrochloride, and reaction accelerators such as triphenylphosphine may be added.
As for content of the hardening accelerator in a resin composition, 0.1-5 mass parts is preferable with respect to 100 mass parts of (A) component + (B) component.

<Soft magnetic metal powder>
Examples of soft magnetic metal powders include those conventionally used in composite magnetic materials, such as pure iron powder, Fe-Si alloy powder, Fe-Si-Al alloy powder, Fe-Ni alloy powder. Fe-Ni-Mo alloy powder, Fe-Ni-Mo-Cu alloy powder, Fe-Co alloy powder, Fe-Ni-Co alloy powder, Fe-Cr alloy powder, Fe-Cr-Si alloy Alloy powder, Fe—Ni—Cr alloy powder, Fe—Cr—Al alloy powder, etc. Among them, Fe—Cr alloy powder such as PC permalloy powder, Fe—Cr alloy powder, Fe—Cr alloy powder, Fe— Si-based alloy powder, Fe-Si-Al-based alloy powder, Fe-Co-based alloy powder, and Fe-Ni-based alloy powder are preferable. The soft magnetic metal powder is obtained by a wet method using a water atomization method, a gas atomization method, a pulverization method, or a chemical treatment.

As the soft magnetic metal powder, a powder obtained by treating the atomized powder with an attritor or a bead mill is preferable. By performing such treatment, the desired average particle diameter or flatness of the soft magnetic metal powder can be obtained.
The average particle size of the soft magnetic metal powder is preferably 30 to 200 μm. When the average particle size is less than the lower limit, the magnetic properties tend to be low, and when the average particle size exceeds the upper limit, it is difficult to maintain a desired shape.

The average particle diameter is a value determined by a laser diffraction / scattering particle diameter / particle size distribution measuring apparatus.
The flatness of the soft magnetic metal powder is preferably a flaky powder of 30 to 200. When the flatness is less than the above lower limit value, the magnetic characteristics tend to be low, and when the flatness exceeds the upper limit value, it is difficult to maintain a desired shape.
Here, the value of “flatness” is represented by L _a / d _a . L _a is the average size of the soft magnetic metal powder, the soft magnetic metal powder and SEM observation from the surface direction to measure the major axis L and the short axis S, but sought the average value (L + S) / 2 is there. d _a is the thickness of the soft magnetic metal powder. The soft magnetic metal powder is embedded in the resin and polished, and the thickness direction of the powder is observed with an optical microscope, and the maximum thickness d _max and the minimum thickness d _min are , And the average value (d _max + d _min ) / 2 is obtained.

  The content of the soft magnetic metal powder in the composite magnetic material can be determined in consideration of the content of the resin composition. Soft magnetic metal powder / [(A) component + (B) component + (C) component] (below , Sometimes referred to as a metal / resin ratio). If the metal / resin ratio is less than the above lower limit, the electromagnetic wave suppression characteristics may be reduced, and if the metal / resin ratio exceeds the above upper limit, the adhesion of the soft magnetic metal powder by the resin composition is insufficient. There is a risk of becoming.

<Arbitrary component in composite magnetic material>
The soft magnetic metal powder is a flame retardant, a flame retardant aid, a filler, a mold release agent, a surface treatment agent, a viscosity modifier, a plasticizer, an antibacterial agent, as long as the effect of the present invention is not impaired. You may contain arbitrary components, such as an antifungal agent, a leveling agent, an antifoamer, a coloring agent, a stabilizer, a coupling agent (henceforth, it is generally called the arbitrary component of a composite magnetic body).
Examples of the flame retardant include conventionally known flame retardants, and include aluminum hydroxide and / or magnesium hydroxide from the viewpoint of halogen-free and further improvement in reflow resistance.

The content of the flame retardant in the composite magnetic body is preferably 40 to 150 parts by mass with respect to 100 parts by mass of the resin composition. If it is less than the lower limit, sufficient flame retardancy may not be obtained, and if it exceeds the upper limit, the adhesion of the soft magnetic metal powder may be insufficient.
Examples of the flame retardant aid include conventionally known flame retardant aids. From the viewpoint of halogen-free, for example, at least one selected from red phosphorus, ammonium polyphosphate, melamine polyphosphate, and phosphate ester is preferable.
The content of the flame retardant aid in the composite magnetic material is preferably 1 to 10 parts by mass with respect to 100 parts by mass of the resin composition. If it is less than the lower limit, sufficient flame retardancy may not be obtained, and if it exceeds the upper limit, heat resistance may be reduced.

(Production method)
The method for producing a composite magnetic body of the present invention includes, for example, a step of obtaining a magnetic coating material in which components (A) to (C) and a soft magnetic metal powder are dispersed in a solvent (paint preparation step), and a magnetic coating material. Is applied to a desired thickness and dried to obtain a semi-cured sheet material (film forming process), and a process of curing the semi-cured sheet material by heating (curing process).
As a method for preparing the magnetic coating material, a conventionally known method can be used. For example, the components (A) to (C) and optional components of the resin composition are added to a solvent, and stirred. A method of adding a soft magnetic metal powder and, if necessary, an optional component of the composite magnetic material to the resin solution and stirring the resin solution may be mentioned. In addition, for example, the components (A) to (C) and the optional component of the resin composition or the optional component of the composite magnetic material are added to the solvent, if necessary, and then the soft magnetic metal powder is added. And stirring.

  Examples of the solvent used in the coating preparation process include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, sulfolane, hexamethylphosphoric triamide, 1,3-dimethyl- 2-imidazolidone, hexane, benzene, toluene, xylene, methyl ethyl ketone, acetone, diethyl ether, tetrahydrofuran, dioxane, 1,2-dimethoxyethane, diethylene glycol dimethyl ether, methyl cellosolve, cellosolve acetate, methanol, ethanol, propanol, isopropanol, methyl acetate, Examples include ethyl acetate, acetonitryl, methylene chloride, chloroform, carbon tetrachloride, chlorobenzene, dichlorobenzene, and dichloroethane. Al, appropriately selected and use the types and amounts so that each component was dissolved.

The content of the solvent in the magnetic coating material is appropriately determined in consideration of the viscosity required for the magnetic coating material.
In the film forming step, a conventionally known film forming method can be used, and examples thereof include a method in which a magnetic coating material is applied to a peelable film at an arbitrary thickness and dried.
Examples of the coating method include a method using a bar coater, a comma coater, a die coater, or the like.
Although the thickness of a semi-hardened sheet material is not specifically limited, For example, 50-500 micrometers is preferable and 50-100 micrometers is more preferable.

Examples of the peelable film include a polypropylene film, a fluororesin film, a polyethylene film, a polyethylene terephthalate (PET) film, paper, and those obtained by subjecting these to a release treatment with a silicone resin (release treatment film).
Although the thickness of a peelable film is not specifically limited, 1-200 micrometers is preferable and 10-50 micrometers is more preferable.
The peelable film preferably has a peel strength of 0.01 to 7.0 g / cm. If the above lower limit is exceeded, the composite magnetic body and the peelable film are not easily peeled off, and the composite magnetic body is easy to handle. If less than the above upper limit, the composite magnetic body is peeled from the peelable film. When this is done, defects and the like do not occur, and manufacturing efficiency increases.

The drying method is not particularly limited as long as it evaporates the solvent in the magnetic coating material applied to the peelable film and brings the resin composition into a semi-cured state. For example, the magnetic material applied to the peelable film The method of heating a coating material at arbitrary temperatures is mentioned.
The heating temperature in the film forming step can be determined in consideration of the components (A) to (C), the type of solvent, and the like.
The heating time in the film forming step can be determined in consideration of the components (A) to (C) and the type of solvent.
The semi-cured sheet material may be immediately subjected to a curing process after drying, or may be stored as a work in progress.
The curing step is a step of heating the semi-cured sheet material to cure the resin composition to obtain a composite magnetic body.
A conventionally known curing method can be used as the curing method, and examples thereof include a method of heating at an arbitrary temperature and a method of heating at an arbitrary temperature while pressing at an arbitrary pressure.
The heating temperature in the curing step can be determined in consideration of the types of the components (A) to (C).
When pressing in the curing step, the pressure is not particularly limited, but is, for example, 5 to 30 MPa.

The composite magnetic body in which the resin composition is in a cured state is cut into a desired dimension and commercialized.
In the curing step, the semi-cured sheet material may be stacked according to the thickness of the final product and cured by, for example, hot pressing to form a composite magnetic body. In the semi-cured sheet product, unreacted phenol resin (derived from component (B)) and unreacted maleimide group (derived from component (C)) remain. For this reason, when the semi-cured sheet material is overlaid and subjected to heat treatment, the (A) component and the (B) component are melted on the contact surface, and the surface tack is developed and adhered.

As needed, you may laminate | stack a new peelable film on the exposed surface of the semi-hardened sheet material or composite magnetic body on a peelable film before or after a hardening process. Thus, by providing the peelable film on both surfaces of the composite magnetic body, it is possible to prevent adhesion of foreign matters.
The composite magnetic body may be provided with a heat resistant adhesive layer on one side or both sides. By providing the heat-resistant adhesive layer, the composite magnetic body can be easily fixed to the object to be pasted.
Examples of the pressure-sensitive adhesive constituting the heat-resistant pressure-sensitive adhesive layer include conventionally known pressure-sensitive adhesives such as a methylphenyl silicone pressure-sensitive adhesive, an addition reaction type silicone pressure-sensitive adhesive, and a peroxide sulfide type silicone pressure-sensitive adhesive.

EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited by these Examples.
Example 1
The molten Fe—Si—Al alloy was gas atomized to obtain a spherical powder having an average particle size of 100 μm. This was put into an attritor and stirred to obtain a soft magnetic metal powder having an average particle diameter of 50 μm, a thickness of 1 μm, and a flatness of 50.
(A) Component: Acrylonitrile-butadiene copolymer having a carboxyl group (Mooney viscosity 60M _{1 + 4} (100 ° C.), acrylonitrile content (AN content) 27 mass%) 10 parts by mass, (B) component: pt- 5 parts by mass of butylphenol type resol phenolic resin (trade name: “CKM-1282”, manufactured by Showa Polymer Co., Ltd.) and copolymer type novolak phenolic resin (CKM-2400: Showa High) of pt-butylphenol and Bis-A 2 parts by mass (manufactured by Molecular Co., Ltd.), (C) component: 3 parts by mass of the compound (1) represented by the above-mentioned formula, and 5 parts by mass of the compound (2) represented by the above-mentioned formula, flame retardant: hydroxylated 25 parts by mass of aluminum and flame retardant aid: 1.5 parts by mass of red phosphorus are added to 100 parts by mass of tetrahydrofuran and stirred, and further 200 parts by mass of the soft magnetic metal powder. In addition, and stirred to obtain a magnetic paint.
The obtained magnetic coating material was applied to the release-treated surface of the release-treated film (PET) so that the thickness after drying was 150 μm, and heated at 150 ° C. for 2 minutes in a hot air circulating dryer, A semi-cured sheet was obtained. The resulting semi-cured sheet was evaluated for laminate properties. Further, in order to improve the orientation of the soft magnetic metal powder, the semi-cured sheet was pressed with a hot press machine at 180 ° C. for 60 minutes at 20 MPa to obtain a composite magnetic body having a thickness of 99 μm. The obtained composite magnetic body was evaluated for magnetic permeability, reflow resistance, flexibility, and internal stress relaxation properties, and the results are shown in Table 1.

(Example 2)
A semi-cured sheet and a composite magnetic body having a thickness of 102 μm were obtained in the same manner as in Example 1 except that a soft magnetic metal powder having an average particle diameter of 30 μm, a thickness of 1 μm, and a flatness of 30 was used. The magnetic susceptibility, reflow resistance, flexibility, lamination property and internal stress relaxation were evaluated, and the results are shown in Table 1.

(Example 3)
A semi-cured sheet and a composite magnetic material having a thickness of 100 μm were obtained in the same manner as in Example 1 except that a soft magnetic metal powder having an average particle size of 50 μm, a thickness of 2 μm, and a flatness of 25 was used. Evaluation was made on reflow resistance, flexibility, laminateability, and internal stress relaxation, and the results are shown in Table 1.

Example 4
A semi-cured sheet material and a composite magnetic material having a thickness of 98 μm were used in the same manner as in Example 1 except that an Fe—Si alloy soft magnetic metal powder having an average particle size of 49 μm, a thickness of 1 μm, and a flatness of 30 was used. A body was obtained and evaluated for magnetic permeability, reflow resistance, flexibility, laminateability, and internal stress relaxation, and the results are shown in Table 1.

(Example 5)
A semi-cured sheet material and a composite magnetic material with a thickness of 98 μm were used in the same manner as in Example 1 except that an Fe—Ni alloy soft magnetic metal powder having an average particle size of 52 μm, a thickness of 1 μm, and a flatness of 52 was used. A body was obtained and evaluated for magnetic permeability, reflow resistance, flexibility, laminateability, and internal stress relaxation, and the results are shown in Table 1.

(Example 6)
A semi-cured sheet and a composite magnetic body having a thickness of 100 μm were obtained in the same manner as in Example 1 except that the soft magnetic metal powder was changed to 125 parts by mass, and the magnetic permeability, reflow resistance, flexibility, and lamination properties were obtained. The internal stress relaxation properties were evaluated, and the results are shown in Table 2.

( Reference Example 7)
A semi-cured sheet in the same manner as in Example 1 except that the component (A) was an acrylonitrile-butadiene copolymer having a Mooney viscosity of 60M _{1 + 4} (100 ° C.) and an AN content of 27% by mass and having no carboxyl group. A composite magnetic material having a thickness of 103 μm was obtained, and magnetic permeability, reflow resistance, flexibility, lamination property, and internal stress relaxation were evaluated. The results are shown in Table 2.

(Example 8)
Semi-cured in the same manner as in Example 1 except that the component (A) is a acrylonitrile-butadiene copolymer having a carboxyl group and having a Mooney viscosity of 75M _{1 + 4} (100 ° C.) and an AN content of 40.5% by mass. A sheet and a composite magnetic material having a thickness of 100 μm were obtained, and magnetic permeability, reflow resistance, flexibility, lamination property, and internal stress relaxation were evaluated. The results are shown in Table 2.

Example 9
(B) A semi-cured sheet and a thickness of 100 μm were the same as in Example 1 except that the component was changed to 7 parts by mass of a pt-butylphenol type resol phenol resin (CKM-1282: manufactured by Showa Polymer Co., Ltd.). The composite magnetic body was obtained and evaluated for magnetic permeability, reflow resistance, flexibility, laminateability, and internal stress relaxation properties, and the results are shown in Table 2.

(Example 10)
Component (B) is a pt-butylphenol type resol phenol resin (trade name: “CKM-1282”, manufactured by Showa Kogyo Co., Ltd.) 4 parts by mass of a copolymer type novolak phenol resin of pt-butylphenol and Bis-A ( CKM-2400 (manufactured by Showa Polymer Co., Ltd.) Except for 3 parts by mass, a semi-cured sheet and a composite magnetic material having a thickness of 100 μm were obtained in the same manner as in Example 1, and permeability, reflow resistance, and flexibility were obtained. Properties, lamination properties, and internal stress relaxation properties were evaluated, and the results are shown in Table 2.

(Example 11)
The component (C) was the same as in Example 1 except that 1.5 parts by mass of the compound (1) represented by the above-described formula and 6.5 parts by mass of the compound (2) represented by the above-described formula were used. A semi-cured sheet and a composite magnetic material having a thickness of 100 μm were obtained, and magnetic permeability, reflow resistance, flexibility, lamination property, and internal stress relaxation were evaluated. The results are shown in Table 3.

(Example 12)
Semi-cured in the same manner as in Example 1 except that 0.25 part by mass of 1,3-bis (3-aminopropyl) -1,1,3,3-tetramethyldisiloxane was added as component (D). A sheet-like sheet and a composite magnetic body having a thickness of 100 μm were obtained and evaluated for magnetic permeability, reflow resistance, flexibility, laminateability, and internal stress relaxation properties, and the results are shown in Table 3.

(Example 13)
(D) Except having added 0.25 mass part of 1, 4- diaminobenzene as a component, it carried out similarly to Example 1, and obtained the semi-hardened sheet material and the 100-micrometer-thick composite magnetic body, magnetic permeability, resistance The reflow property, flexibility, lamination property, and internal stress relaxation property were evaluated, and the results are shown in Table 3.

(Comparative Example 1)
A semi-cured sheet and a composite magnetic body having a thickness of 100 μm were obtained in the same manner as in Example 1 except that chlorinated polyethylene (chlorinated PE) was used instead of the components (A) to (C). The magnetic permeability, reflow resistance, flexibility, lamination property, and internal stress relaxation were evaluated, and the results are shown in Table 3.

(Comparative Example 2)
(A) It is the same as in Example 1 except that the component is not used, flame retardant: 15 parts by weight of aluminum hydroxide, flame retardant aid: 0.9 part by weight of red phosphorus, and 120 parts by weight of soft magnetic metal powder. Thus, a semi-cured sheet and a composite magnetic body having a thickness of 100 μm were obtained, and magnetic permeability, reflow resistance, flexibility, laminateability, and internal stress relaxation were evaluated. The results are shown in Table 3.

(Comparative Example 3)
(B) The same procedure as in Example 1 was used, except that the component was not used, flame retardant: 18 parts by weight of aluminum hydroxide, flame retardant aid: 1.2 parts by weight of red phosphorus, and 144 parts by weight of soft magnetic metal powder. Thus, a semi-cured sheet and a composite magnetic body having a thickness of 100 μm were obtained, and magnetic permeability, reflow resistance, flexibility, laminateability, and internal stress relaxation were evaluated. The results are shown in Table 3.

(Comparative Example 4)
(C) Without using the component, flame retardant: 17 parts by weight of aluminum hydroxide, flame retardant aid: 1 part by weight of red phosphorus, 136 parts by weight of soft magnetic metal powder, the same as in Example 1, A semi-cured sheet and a composite magnetic body having a thickness of 100 μm were obtained, and magnetic permeability, reflow resistance, flexibility, lamination property, and internal stress relaxation were evaluated. The results are shown in Table 3.

(Evaluation method)
The evaluation of the magnetic permeability, reflow resistance, flexibility, lamination property, and internal stress relaxation in Tables 1 to 3 below was performed by the following evaluation methods.
<Permeability>
For the composite magnetic body of each example, a real term and an imaginary term are obtained, and those having a real term of 80 or more and an imaginary term of 20 or more are regarded as “good”, and those having a real number less than 80 or less than the imaginary term 20 are rejected. ".
(Real term of permeability)
The composite magnetic material of each example was punched into a ring shape having an outer diameter of 7 mm and an inner diameter of 3 mm, and this was wound with 12 turns to obtain a test piece. About this test piece, it calculated with the impedance in 1 MHz using the impedance measuring instrument "Precision Impedance Analyzer HP4294A" by Agilent Technologies.
(Imaginary term of permeability)
Using the S-parameter measuring device “Network Analyzer E5071C” manufactured by Agilent Technologies, the loss term is measured in the range of 1 MHz to 10 GHz, and the maximum value is an imaginary number. Term.

<Reflow resistance>
The composite magnetic material of each example was used as a 50 mm long × 50 mm wide test piece. The test piece was subjected to a solder reflow test (twice at 260 ° C. for 10 seconds × 2 times) in accordance with JIS C-5012 “Test method for printed wiring board” 10.4.1 “Solder float method”. The test piece after the solder reflow test was observed with the naked eye and evaluated according to the following evaluation criteria.
[Evaluation criteria]
A: No change in appearance is observed before and after the reflow test.
○: Almost no change in appearance was observed before and after the reflow test.
Δ: Strain is observed after the reflow test, but swelling, powdering, cracking and cracking are not observed.
X: Swelling, powdering, cracking or cracking is observed before and after the reflow test.

<Flexibility>
The composite magnetic material of each example was used as a 50 mm long × 50 mm wide test piece. The test piece was subjected to a solder reflow test (twice at 260 ° C. for 10 seconds × 2 times) in accordance with JIS C-5012 “Test method for printed wiring board” 10.4.1 “Solder float method”. The test pieces before and after the solder reflow test were bent with a MIT anti-fatigue testing machine, model number: DA, manufactured by Toyo Seiki Seisakusho Co., Ltd., with a bending speed of 175 times / minute, a bending angle of 135 °, and a load of 4.9 N. It was. The test piece after bending was observed with the naked eye and evaluated according to the following evaluation criteria.
[Evaluation criteria]
A: No whitening, cracks or cracks are observed at the bent part.
○: Cracks and cracks are not observed in the bent part, but whitening is observed.
Δ: Cracks or cracks are observed in the bent portion.
X: It cut | disconnected by the bending part.

<Laminability>
Three semi-cured sheets of each example were stacked and subjected to hot pressing at 150 ° C. and 20 MPa for 10 seconds. After the hot pressing, the composite magnetic body was visually observed, and the adhesion state was evaluated according to the following evaluation criteria.
[Evaluation criteria]
(Double-circle): The boundary of each layer is not recognized but it has become one composite magnetic body as a whole.
○: The boundary of each layer is recognized, but each layer is in close contact and does not peel off.
(Triangle | delta): The boundary of each layer is recognized and each layer can be peeled with fingers.
X: Each layer is separated and separated (efficient production is impossible).

<Internal stress relaxation>
The composite magnetic material of each example was bonded to a commercially available glass epoxy-printed wiring board at 150 ° C., and then pressed at 150 ° C. and 20 MPa with a hot press machine to obtain a test piece. This sample piece was subjected to a thermal cycle test of 10 cycles, with 150 ° C. × 2 hours and −40 ° C. × 2 hours as one cycle. The test piece after the heat cycle test was observed with the naked eye and evaluated according to the following evaluation criteria.
[Evaluation criteria]
A: No change in appearance was observed before and after the thermal cycle test.
○: Almost no change in appearance was observed before and after the thermal cycle test.
(Triangle | delta): Although distortion is recognized after a heat cycle test, a swelling, powdering, a crack, and a crack are not recognized.
X: Swelling, cracking or cracking is observed before and after the reflow test.

As shown in Table 1 , Table 2, and Table 3 , Examples 1 to 6, 8 to 13 and Reference Example 7 to which the present invention is applied all have a magnetic permeability of “◯”, and are generated from electronic devices and the like. The electromagnetic wave noise could be sufficiently absorbed. In addition, Examples 1 to 6 and 8 to 13 and Reference Example 7 had an internal stress relaxation property of “、”, and quality deterioration hardly occurred even in long-term use. Further, in Examples 1 to 6, 8 to 13, and Reference Example 7 , the reflow resistance, flexibility, and lamination property were “◎”.
Comparative Example 1 in which the resin composition was made of chlorinated polyethylene and Comparative Example 4 in which the component (C) was not used were “x” in reflow resistance, and after solder reflow, deformation was significant and flexibility could not be evaluated. It was. Moreover, the comparative example 2 which did not use (A) component was "x" in a softness | flexibility, lamination property, and internal stress relaxation, and it was difficult to make a composite magnetic body into a sheet and lamination. In Comparative Example 3 in which the component (B) was not used, the lamination property was “x”, and a composite magnetic body could not be produced with high production efficiency.
From these results, it was found that by applying the present invention, it is possible to obtain a composite magnetic body that has sufficient flexibility and does not cause a defective shape in reflow soldering and can be manufactured with high manufacturing efficiency.

Claims (16)

Component (A): Acrylonitrile-butadiene copolymer having carboxyl group, Component (B): Phenolic resin, Component (C): Compound (1) containing two or more maleimide groups represented by the following formula And a soft magnetic metal powder dispersed in a resin composition containing the compound (2).

The soft magnetic metal powder is a flaky powder having an average particle diameter of 30 to 200 µm and a flatness of 30 to 200 obtained by flattening an atomized powder made of a soft magnetic metal or alloy. Composite magnetic material. The soft magnetic powder is Fe-Si based alloy powder, Fe-Si-Al based alloy powder, Fe-Ni based alloy powder, Fe-Ni-Mo based alloy powder, Fe-Ni-Mo-Cu based alloy powder, Fe The composite magnetic body according to claim 1, wherein the composite magnetic body is at least one selected from —Cr-based alloy powder. 2. The composite magnetic body according to claim 1, wherein a mass ratio represented by the soft magnetic metal powder / [(A) component + (B) component + (C) component] is 2-19. 2. The composite magnetic body according to claim 1, wherein the component (A) is an acrylonitrile-butadiene copolymer of 5 to 50% by mass of acrylonitrile. The composite magnetic body according to claim 1 , wherein the acrylonitrile-butadiene copolymer having a carboxyl group has a Mooney viscosity of 50 to 90 M _{1 + 4} (100 ° C.). The composite magnetic body according to claim 1, wherein the component (B) is a phenol resin containing a resol-type alkylphenol. The composite magnetic body according to claim 1, wherein the component (B) uses a resol type phenol and a novolac type phenol in combination. 2. The composite magnetic body according to claim 1, wherein the component (C) has a mass ratio of 1 to 15 represented by compound (2) / compound (1). The mass ratio represented by (A) component / [(B) component + (C) component] is 0.1 to 10, and (B) component / [(B) component + (C) component]. 2. The composite magnetic body according to claim 1, wherein a mass ratio represented by the formula is 0.1 to 0.9. 2. The composite magnetic body according to claim 1, further comprising (D) component: diamine compound in addition to the (A) component, (B) component, and (C) component. The composite magnetic body according to claim 11 , wherein the component (D) is a compound (3) represented by the following formula.

(Wherein R ¹ represents a divalent aromatic group) The composite magnetic body according to claim 11 , wherein the component (D) is a compound (4) represented by the following formula having a weight average molecular weight of 200 to 7,000.

(Wherein R ² represents a propylene group or a phenoxymethylene group, and n represents an integer of 0 to 7) A flame retardant aid comprising a flame retardant comprising aluminum hydroxide and / or magnesium hydroxide having an average particle size of 0.1 to 3 μm, and at least one selected from red phosphorus, ammonium polyphosphate, melamine polyphosphate, and phosphate ester The composite magnetic body according to claim 1, comprising: The mass ratio represented by the flame retardant / [(A) component + (B) component + (C) component] is 0.4 to 1.5, and the flame retardant aid / [(A) component + The composite magnetic body according to claim 14 , wherein a mass ratio represented by (B) component + (C) component] is 0.01 to 0.1. 2. The composite magnetic body according to claim 1, wherein a heat resistant adhesive layer is laminated on one side or both sides of the composite magnetic body.