JP2022118537A - Magnetic material, magnetic member, coil, and inductor wiring board - Google Patents

Abstract

To provide a magnetic material capable of forming an insulating layer having high magnetic permeability in a frequency range of 1 MHz to 1 GHz, a small loss factor, and excellent insulating reliability.SOLUTION: A magnetic material contains a magnetic powder A and a polymer B having at least one type of repeating unit among repeating units represented by formulas 1-1, 1-2, and 1-3. [R1 is each independently a halogen atom, a C1-20 hydrocarbon group, a C1-20 halogenated hydrocarbon group, a group partially substituted with at least one selected from O and S, a nitro group, a cyano group, and an amino group or a salt of an amino group, n is each independently an integer of 0 to 2, A1 and A2 are each independently -O-, -S- or -N(R2)-[R2 is a hydrogen atom, a C1-20 monovalent hydrocarbon group, a C1-20 monovalent halogenated hydrocarbon group, etc.], and X is an organic group.]SELECTED DRAWING: None

Description

The present invention relates to magnetic materials, magnetic members, coils and inductor wiring boards.

A large number of inductor elements called power inductors, high-frequency inductors, and common mode choke coils are installed in information terminals such as mobile phones and smartphones. At present, the structures of inductor elements for high-frequency bands in which the frequency of the operating signal is 1 MHz or more, particularly in the range of 10 MHz to 1 GHz, include, for example, a winding structure in which a coil is wound around a core member, and a laminated structure in which a coil conductor is laminated on a core member. Structure: A wiring layer forming a part of the coil is formed on each of a plurality of layered insulating layers, and the insulating layers on which the wiring layers are formed are stacked so that the wiring layers are electrically connected to each other for insulation. Film structures are known in which coils are built into the thickness of the part.

An inductor element for a high frequency band generally employs an air-core coil, that is, a structure in which the core is hollow or filled with a non-magnetic material, because a high Q value is required as a characteristic. However, since the core of the inductor element for a high frequency band having such a structure is non-magnetic, it is impossible to increase the magnetic permeability (relative magnetic permeability) of the core. There is a drawback that the inductance (L value) decreases when operated in a high frequency band.

Patent Document 1 discloses that if a thermosetting magnetic slurry containing (A) an alicyclic olefin polymer having a carboxyl group, (B) a thermosetting agent, (C) a magnetic substance, and (D) a solvent is used, (C) It is disclosed that the magnetic material has excellent dispersibility, each component can be contained at a high concentration, and an electrical insulating layer having excellent properties such as electrical insulation, high frequency characteristics, and magnetic permeability can be formed.

WO2004/29153

Due to the recent demand for thinner and smaller information terminals, inductor elements for high frequency bands are also required to be thinner and smaller.

In order to further reduce the thickness and size of the high-frequency band inductor element, it is necessary to reduce the number of turns of the coil and reduce the cross-sectional area of the wiring that constitutes the coil. In order to reduce the number of turns of the coil and to reduce the cross-sectional area of the wiring that constitutes the coil, the inductor element for a high frequency band having the film structure is advantageous. However, in a high-frequency band inductor element with a film structure, simply reducing the number of turns of the coil and reducing the cross-sectional area of the wiring that constitutes the coil results in a decrease in inductance. On the other hand, in a high frequency band inductor element with a film structure, if the magnetic permeability (μ′) of the insulating layer can be increased, the L value and Q value of the high frequency band inductor element can be improved. Therefore, there is a demand for a material that can increase the magnetic permeability of the insulating layer and reduce the loss factor.

However, when an inductor element having a film structure is formed using the thermosetting magnetic slurry according to Patent Document 1, the loss factor (μ''/μ') increases particularly in the frequency range of 1 MHz to 1 GHz. There is a risk of Therefore, it is difficult to say that the material disclosed in Patent Document 1 is useful as a material for an insulating layer (insulating portion) of an inductor element for a high frequency band.

The present invention has been made in view of the above problems, and is capable of forming an insulating layer having high magnetic permeability in the frequency range of 1 MHz to 1 GHz, a small loss factor, and excellent insulating reliability. Intended to provide material.

As a result of intensive studies aimed at solving the above problems, the inventors of the present invention have found that the above problems can be solved according to the following configuration example.
A configuration example of the present invention is as follows.

[1] A magnetic powder (A) and a polymer (B) having at least one type of repeating unit among repeating units represented by the following formulas (1-1), (1-2) and (1-3) A magnetic material containing

〔式（１－１）～（１－３）中、Ｒ¹はそれぞれ独立して、ハロゲン原子、炭素数１～２０の１価の炭化水素基、炭素数１～２０の１価のハロゲン化炭化水素基、これら炭化水素基若しくはハロゲン化炭化水素基における一部が酸素原子及び硫黄原子から選ばれる少なくとも１つで置換された基、ニトロ基、シアノ基、アミノ基、又は、アミノ基の塩である。ｎはそれぞれ独立して、０～２の整数である。ｎが２の場合、複数のＲ¹は、同一であっても異なっていてもよく、任意の組み合わせで結合して環構造の一部を形成していてもよい。Ａ¹及びＡ²はそれぞれ独立して、－Ｏ－、－Ｓ－又は－Ｎ（Ｒ²）－である［Ｒ²は、水素原子、炭素数１～２０の１価の炭化水素基、炭素数１～２０の１価のハロゲン化炭化水素基又はこれら炭化水素基若しくはハロゲン化炭化水素基における一部が酸素原子及び硫黄原子から選ばれる少なくとも１つで置換された基である。］。Ｘは２価の有機基である。〕

[In formulas (1-1) to (1-3), R ¹ is each independently a halogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, or a monovalent halogenated group having 1 to 20 carbon atoms. Hydrocarbon groups, groups partially substituted with at least one selected from oxygen atoms and sulfur atoms in these hydrocarbon groups or halogenated hydrocarbon groups, nitro groups, cyano groups, amino groups, or salts of amino groups is. Each n is independently an integer of 0-2. When n is 2, multiple R ¹ may be the same or different, and may be combined in any combination to form part of the ring structure. A ¹ and A ² are each independently -O-, -S- or -N(R ² )- [R ² is a hydrogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, a carbon It is a monovalent halogenated hydrocarbon group of number 1 to 20, or a group partially substituted with at least one selected from oxygen and sulfur atoms in these hydrocarbon groups or halogenated hydrocarbon groups. ]. X is a divalent organic group. ]

[2] The magnetic material is
A magnetic composition containing the magnetic powder (A) and the polymer (B), or
A magnetic filler comprising the magnetic powder (A) and a coating layer containing the polymer (B) covering the magnetic powder (A).
The magnetic material according to [1].

[3] The magnetic material according to [1] or [2], wherein X in formulas (1-1) to (1-3) contains a group represented by formula (2-1) below.

〔式（２－１）中、Ａｒ₁及びＡｒ₂はそれぞれ独立して、置換若しくは非置換の芳香族炭化水素基である。Ｌは、単結合、－Ｏ－、－Ｓ－、－Ｎ（Ｒ⁸）－、－Ｃ（Ｏ）－、－Ｃ（Ｏ）－Ｏ－、－Ｃ（Ｏ）－ＮＨ－、－Ｓ（Ｏ）－、－Ｓ（Ｏ）₂－、－Ｐ（Ｏ）－、又は、２価の有機基である［Ｒ⁸は、水素原子、炭素数１～２０の１価の炭化水素基、又は、炭素数１～２０の１価のハロゲン化炭化水素基である。］。ｙは、０～５の整数である。ｙが２以上の場合、複数のＬは、それぞれ同一であっても異なっていてもよい。Ｒ⁶及びＲ⁷はそれぞれ独立して、単結合、メチレン基、又は、炭素数２～４のアルキレン基である。〕

[In formula (2-1), Ar ₁ and Ar ₂ are each independently a substituted or unsubstituted aromatic hydrocarbon group. L is a single bond, -O-, -S-, -N(R ⁸ )-, -C(O)-, -C(O)-O-, -C(O)-NH-, -S( O)-, -S(O) ₂ -, -P(O)-, or a divalent organic group [R ⁸ is a hydrogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, or , is a monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms. ]. y is an integer from 0 to 5; When y is 2 or more, a plurality of L's may be the same or different. R ⁶ and R ⁷ are each independently a single bond, a methylene group, or an alkylene group having 2 to 4 carbon atoms. ]

[4] The magnetic material according to any one of [1] to [3], wherein the magnetic powder (A) contains an iron element.

[5] The magnetic material according to [2], wherein the magnetic composition or the coating layer further contains a curable compound (C) and a curing aid (D).
[6] The curable compound (C) is at least one selected from the group consisting of epoxy compounds, cyanate ester compounds, vinyl compounds, silicone compounds, oxazine compounds, maleimide compounds, allyl compounds, oxetane compounds, methylol compounds and propargyl compounds. The magnetic material according to [5], which is a seed.

[7] The magnetic material according to [2], wherein the magnetic composition further contains a solvent (E).

[8] A magnetic member formed from the magnetic material according to any one of [1] to [7].
[9] A coil including the magnetic member according to [8].
[10] An inductor wiring board including the magnetic member according to [8] or the coil according to [9].

According to the present invention, it is possible to provide an insulating layer that has high magnetic permeability, a small loss factor, and excellent insulating reliability, particularly in the frequency range of 1 MHz to 1 GHz. A wiring board having an inductor element for a high frequency band can be provided by a simple process.

Preferred embodiments of the present invention will be described in detail below. It should be understood that the present invention is not limited only to the embodiments described below, but includes various modifications implemented without departing from the gist of the present invention.
In the present specification, a numerical range described using "to" means that the numerical values described before and after "to" are included as lower and upper limits.

1. Magnetic Material A magnetic material according to one embodiment of the present invention (hereinafter also referred to as "this material") comprises a magnetic powder (A) and the following formulas (1-1), (1-2) and (1-3) and a polymer (B) having at least one repeating unit among the repeating units represented by

〔式（１－１）～（１－３）中、Ｒ¹はそれぞれ独立して、ハロゲン原子、炭素数１～２０の１価の炭化水素基、炭素数１～２０の１価のハロゲン化炭化水素基、これら炭化水素基若しくはハロゲン化炭化水素基における一部が酸素原子及び硫黄原子から選ばれる少なくとも１つで置換された基、ニトロ基、シアノ基、アミノ基、又は、アミノ基の塩である。ｎはそれぞれ独立して、０～２の整数である。ｎが２の場合、複数のＲ¹は、同一であっても異なっていてもよく、任意の組み合わせで結合して環構造の一部を形成していてもよい。Ａ¹及びＡ²はそれぞれ独立して、－Ｏ－、－Ｓ－又は－Ｎ（Ｒ²）－である［Ｒ²は、水素原子、炭素数１～２０の１価の炭化水素基、炭素数１～２０の１価のハロゲン化炭化水素基又はこれら炭化水素基若しくはハロゲン化炭化水素基における一部が酸素原子及び硫黄原子から選ばれる少なくとも１つで置換された基である。］。Ｘは２価の有機基である。〕

[In formulas (1-1) to (1-3), R ¹ is each independently a halogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, or a monovalent halogenated group having 1 to 20 carbon atoms. Hydrocarbon groups, groups partially substituted with at least one selected from oxygen atoms and sulfur atoms in these hydrocarbon groups or halogenated hydrocarbon groups, nitro groups, cyano groups, amino groups, or salts of amino groups is. Each n is independently an integer of 0-2. When n is 2, multiple R ¹ may be the same or different, and may be combined in any combination to form part of the ring structure. A ¹ and A ² are each independently -O-, -S- or -N(R ² )- [R ² is a hydrogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, a carbon It is a monovalent halogenated hydrocarbon group of number 1 to 20, or a group partially substituted with at least one selected from oxygen and sulfur atoms in these hydrocarbon groups or halogenated hydrocarbon groups. ]. X is a divalent organic group. ]

The form of this material is not particularly limited, but preferred examples thereof include:
a magnetic composition containing the magnetic powder (A) and the polymer (B) (hereinafter also referred to as "this composition");
A magnetic filler comprising the magnetic powder (A) and a coating layer containing the polymer (B) covering the magnetic powder (A) (hereinafter also referred to as "the present filler")
are mentioned.
The present composition or the coating layer may further contain a curable compound (C) and a curing aid (D).

<Magnetic powder (A)>
The magnetic powder (A) preferably contains Fe element. Examples of the magnetic powder (A) include pure iron powder, Fe--Si alloy powder, Fe--Si--Al alloy powder, Fe--Cr alloy powder, Fe--Cr--Si alloy powder, and Fe--Ni. -Cr-based alloy powder, Fe--Cr--Al-based alloy powder, Fe--Ni-based alloy powder, Fe--Ni--Mo-based alloy powder, Fe--Ni--Mo--Cu-based alloy powder, Fe--Co-based alloy powder, or Fe alloys such as Fe-Ni-Co alloy powder, amorphous alloys such as Fe-based amorphous, Co-based amorphous, Mg-Zn ferrite, Mn-Zn ferrite, Mn-Mg ferrite, Cu-Zn ferrite , Mg-Mn-Sr ferrite, Ni-Zn ferrite and other spinel ferrites, Ba-Zn ferrite, Ba-Mg ferrite, Ba-Ni ferrite, Ba-Co ferrite, Ba-Ni-Co Hexagonal ferrites such as system ferrites and garnet type ferrites such as Y system ferrites can be mentioned. Among these, as the magnetic powder (A), Fe—Si alloy powder, Fe—Si—Al alloy powder, Fe—Cr alloy powder, Fe—Cr—Si alloy powder, Fe—Ni—Cr system Fe alloys containing one or more elements selected from Si, Al, and Cr, such as alloy powders and Fe--Cr--Al alloy powders, are preferred, and Fe alloys containing Si and Cr are more preferred.

A commercially available magnetic powder can be used as the magnetic powder (A). Specific examples of the commercially available magnetic powder include "PST-S" manufactured by Sanyo Special Steel Co., Ltd., "AW2-08" manufactured by Epson Atmix Corporation, "AW2-08PF20F", "AW2-08PF10F", " AW2-08PF8F", "AW2-08PF3F", "Fe-3.5Si-4.5CrPF20F", "Fe-50NiPF20F", "Fe-80Ni-4MoPF20F", JFE Chemical Co., Ltd. "LD-M", " LD-MH", "KNI-106", "KNI-106GSM", "KNI-106GS", "KNI-109", "KNI-109GSM", "KNI-109GS", manufactured by Toda Kogyo Co., Ltd. "KNS- 415", "BSF-547", "BSF-029", "BSN-125", "BSN-714", "BSN-828", "S-1281", "S-1641", "S-1651" , "S-1470", "S-1511", "S-2430", "JR09P2" manufactured by Japan Heavy Chemical Industries, Ltd., "Nanotek" manufactured by CIK Nanotech Co., Ltd., "JEMK-S manufactured by Kinseimatec Co., Ltd. ”, “JEMK-H”, and “Yttriumironoxide” manufactured by SIGMA-ALDRICH.

The magnetic powder (A) may be used singly, or two or more kinds of particles having different average particle sizes and types may be used. Appropriate use of fillers with different particle sizes increases the fluidity of the present composition and enhances the fillability of the magnetic powder (A) in the present filler.

The average particle size of the magnetic powder (A) is preferably more than 0.1 μm, more preferably more than 0.1 μm and 100 μm or less, still more preferably 0.2 to 70 μm, particularly preferably 0.5 to 50 μm. be.
When the average particle diameter is within the above range, the fluidity of the present composition is further enhanced, thereby enabling shape control in irregularities and the like, and reducing the loss factor while maintaining high magnetic permeability of the molded body. .
The average particle size in this specification refers to D50 measured after performing ultrasonic dispersion treatment for 2 minutes in a batch cell using SALD2300 manufactured by Shimadzu Corporation and using toluene as a dispersion solvent.

The magnetic powder (A) may be surface-treated powder. The surface treatment refers to an operation for modifying the powder surface. Examples of this operation include treating the surface of the powder with a coupling agent and plasma treating the powder. Magnetic powder (A) having functional groups on part or all of the surface can be obtained by such a surface treatment.

Examples of the functional group include residues formed by surface treatment with known coupling agents such as silane-based coupling agents, titanium-based coupling agents, aluminum-based coupling agents, and zirconium-based coupling agents. , a silane-based coupling agent, and a titanium-based coupling agent.
By using the magnetic powder (A) having functional groups on part or all of the surface, the bond between the magnetic powder (A) and the polymer (B) can be strengthened, and the fluidity of the present composition can be improved. can be enhanced.

When obtaining the magnetic powder (A) having functional groups on part or all of the surface as described above, plasma treatment may be performed in advance as part of the surface treatment, and then the functional groups may be formed. For example, by applying oxygen plasma treatment, OH groups are generated on the surface of the powder, which facilitates bonding between the powder and the residues of the coupling agent via oxygen atoms, and further strengthens the functional groups. can be combined.
In the magnetic powder (A), it is possible to confirm, for example, with a Fourier transform infrared spectrophotometer that the powder and the residue of the coupling agent are bonded via oxygen atoms.

Further, another coating treatment may be applied to the base of the surface treatment described above. Examples of such coating treatment include resin coating such as silicone resin, silica coating, and the like. By applying such a coating treatment, the insulating properties of the magnetic powder (A) can be further enhanced. Such coating treatment may be applied as required. This coating treatment may be performed alone instead of as a base for the surface treatment described above.

The volume fraction of the magnetic powder (A) is 100% by volume of solids constituting the present material (e.g. 100% by volume of solids in the present composition; the total solid content of the magnetic powder (A) and the coating layer in the present filler). 100% by volume), preferably 35 to 99% by volume, more preferably 40 to 95% by volume.
When the volume fraction of the magnetic powder (A) is within the above range, the content of the magnetic powder (A) is sufficiently high, so that the present material having good magnetic properties can be obtained.
When the volume fraction of the magnetic powder (A) is at least the lower limit, it is possible to prevent the magnetic properties of the present material from deteriorating due to the magnetic properties of the magnetic powder (A). On the other hand, if the volume fraction of the magnetic powder (A) is less than the above upper limit, the volume fraction of the polymer (B) will be relatively low, and the flowability of the present composition will be reduced. It is possible to suppress deterioration of mechanical properties after hardening the material.

<Polymer (B)>
The polymer (B) has at least one type of repeating unit among repeating units represented by the following formulas (1-1), (1-2) and (1-3).
The polymer (B) contained in this material may be of one type or two or more types.

〔式（１－１）～（１－３）中、Ｒ¹はそれぞれ独立して、ハロゲン原子、炭素数１～２０の１価の炭化水素基、炭素数１～２０の１価のハロゲン化炭化水素基、これら炭化水素基若しくはハロゲン化炭化水素基における一部が酸素原子及び硫黄原子から選ばれる少なくとも１つで置換された基、ニトロ基、シアノ基、アミノ基、又は、アミノ基の塩である。ｎはそれぞれ独立して、０～２の整数である。ｎが２の場合、複数のＲ¹は、同一であっても異なっていてもよく、任意の組み合わせで結合して環構造の一部を形成していてもよい。Ａ¹及びＡ²はそれぞれ独立して、－Ｏ－、－Ｓ－又は－Ｎ（Ｒ²）－である［Ｒ²は、水素原子、炭素数１～２０の１価の炭化水素基、炭素数１～２０の１価のハロゲン化炭化水素基又はこれら炭化水素基若しくはハロゲン化炭化水素基における一部が酸素原子及び硫黄原子から選ばれる少なくとも１つで置換された基である。］。Ｘは２価の有機基である。〕

[In formulas (1-1) to (1-3), R ¹ is each independently a halogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, or a monovalent halogenated group having 1 to 20 carbon atoms. Hydrocarbon groups, groups partially substituted with at least one selected from oxygen atoms and sulfur atoms in these hydrocarbon groups or halogenated hydrocarbon groups, nitro groups, cyano groups, amino groups, or salts of amino groups is. Each n is independently an integer of 0-2. When n is 2, multiple R ¹ may be the same or different, and may be combined in any combination to form part of the ring structure. A ¹ and A ² are each independently -O-, -S- or -N(R ² )- [R ² is a hydrogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, a carbon It is a monovalent halogenated hydrocarbon group of number 1 to 20, or a group partially substituted with at least one selected from oxygen and sulfur atoms in these hydrocarbon groups or halogenated hydrocarbon groups. ]. X is a divalent organic group. ]

Halogen atoms for R ¹ include, for example, fluorine, chlorine, bromine and iodine atoms.

The monovalent hydrocarbon group having 1 to 20 carbon atoms for R ¹ includes, for example, a monovalent chain hydrocarbon group, a monovalent alicyclic hydrocarbon group, and a monovalent aromatic hydrocarbon group. .

Examples of the monovalent chain hydrocarbon group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group and n-pentyl group. alkenyl groups such as ethenyl group, propenyl group, butenyl group and pentenyl group; and alkynyl groups such as ethynyl group, propynyl group, butynyl group and pentynyl group.

Examples of the monovalent alicyclic hydrocarbon group include monocyclic cycloalkyl groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group and cyclohexyl group; polycyclic cycloalkyl groups such as norbornyl group and adamantyl group; monocyclic cycloalkenyl groups such as cyclopropenyl group, cyclobutenyl group, cyclopentenyl group and cyclohexenyl group; and polycyclic cycloalkenyl groups such as norbornenyl group.

Examples of the monovalent aromatic hydrocarbon group include aryl groups such as phenyl group, tolyl group, xylyl group, naphthyl group and anthryl group; aralkyl groups such as benzyl group, phenethyl group, phenylpropyl group and naphthylmethyl group; are mentioned.

The monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms for R ¹ includes, for example, a part or all of the hydrogen atoms in the above monovalent hydrocarbon group having 1 to 20 carbon atoms being fluorine atoms, chlorine atoms, A group substituted with a halogen atom such as a bromine atom and an iodine atom can be mentioned.

R ¹ is a monovalent hydrocarbon group having 1 to 20 carbon atoms or a monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms, and a portion thereof is substituted with at least one selected from an oxygen atom and a sulfur atom. Specific examples include groups in which part of the hydrocarbon group or halogenated hydrocarbon group is substituted with —O—, —S—, an ester group or a sulfonyl group. .

The amino group for R ¹ is not particularly limited, and may be a primary amino group (--NH ₂ ), a secondary amino group (--NHR), or a tertiary amino group (--NR ₂ ).
The substituent (R) in the secondary amino group and the tertiary amino group in R ¹ is not particularly limited, and examples thereof include the above-mentioned monovalent hydrocarbon groups having 1 to 20 carbon atoms.
The anion that constitutes the anion site in the salt of the amino group is not particularly limited, and includes known anions such as ^Cl.sup.- .

R ¹ is a halogen atom having 1 to 6 carbon atoms, from the viewpoint of synthesizing the polymer (B) with good polymerization reactivity and improving the solubility of the monomer that is the raw material of the polymer (B). A monovalent hydrocarbon group, a monovalent halogenated hydrocarbon group having 1 to 6 carbon atoms, a nitro group, a cyano group, an amino group, or a salt of an amino group is preferable, a fluorine atom, a chlorine atom, a methyl group, a nitro group, cyano group, tert-butyl group, phenyl group and primary amino group are more preferred. From the same point of view, n is preferably 0 or 1, more preferably 0.

The pyridazine ring in the formula (1-1), the pyrimidine ring in the formula (1-2), and the two bonds that bond to the pyrazine ring in the formula (1-3) (a bond that bonds to A ¹ and A ² Although the position of the bond that binds to (B) is not particularly limited, the meta position is preferable from the viewpoint of synthesizing the polymer (B) with good polymerization reactivity.

Among the repeating units represented by the formulas (1-1) to (1-3), the polymer (B) can be synthesized with good polymerization reactivity, and the polymer has excellent solubility in various organic solvents. A repeating unit having a pyrimidine skeleton and represented by the above formula (1-2) is preferable from the viewpoint that (B) can be easily obtained.

Examples of monomers that are raw materials for the repeating units represented by the above formulas (1-1) to (1-3) (monomers that are raw materials for portions containing a pyridazine ring, a pyrimidine ring, or a pyrazine ring) include: , 4,6-dichloropyrimidine, 4,6-dibromopyrimidine, 2,4-dichloropyrimidine, 2,5-dichloropyrimidine, 2,5-dibromopyrimidine, 5-bromo-2-chloropyrimidine, 5-bromo-2 -fluoropyrimidine, 5-bromo-2-iodopyrimidine, 2-chloro-5-fluoropyrimidine, 2-chloro-5-iodopyrimidine, 2,4-dichloro-5-fluoropyrimidine, 2,4-dichloro-5- iodopyrimidine, 5-chloro-2,4,6-trifluoropyrimidine, 2,4,6-trichloropyrimidine, 4,5,6-trichloropyrimidine, 2,4,5-trichloropyrimidine, 2,4,5, 6-tetrachloropyrimidine, 2-phenyl-4,6-dichloropyrimidine, 2-methylthio-4,6-dichloropyrimidine, 2-methylsulfonyl-4,6-dichloropyrimidine, 5-methyl-4,6-dichloropyrimidine , 2-amino-4,6-dichloropyrimidine, 5-amino-4,6-dichloropyrimidine, 2,5-diamino-4,6-dichloropyrimidine, 4-amino-2,6-dichloropyrimidine, 5-methoxy -4,6-dichloropyrimidine, 5-methoxy-2,4-dichloropyrimidine, 5-fluoro-2,4-dichloropyrimidine, 5-bromo-2,4-dichloropyrimidine, 5-iodo-2,4-dichloro pyrimidine, 2-methyl-4,6-dichloropyrimidine, 6-methyl-2,4-dichloropyrimidine, 5-methyl-2,4-dichloropyrimidine, 5-nitro-2,4-dichloropyrimidine, 4-amino- 2-chloro-5-fluoropyrimidine, 2-methyl-5-amino-4,6-dichloropyrimidine, 5-bromo-4-chloro-2-methylthiopyrimidine; 3,6-dichloropyridazine, 3,5-dichloropyridazine , 4-methyl-3,6-dichloropyridazine; 2,3-dichloropyrazine, 2,6-dichloropyrazine, 2,5-dibromopyrazine, 2,6-dibromopyrazine, 2-amino-3,5-dibromopyrazine , 5,6-dicyano-2,3-dichloropyrazine. In addition, these monomers may be used individually by 1 type, and may use 2 or more types.

A ¹ and A ² in the above formulas (1-1), (1-2) and (1-3) are each independently -O-, -S- or -N(R ² )- . When A ¹ and A ² are —O—, it is preferred from the viewpoint of flexibility, solubility and heat resistance. When A ¹ and A ² are --N(R ² )--, it is preferable in terms of adhesion and the like.

R ² is a hydrogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, a monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms, or part of these hydrocarbon groups or halogenated hydrocarbon groups is oxygen; It is a group substituted with at least one selected from atoms and sulfur atoms.
Examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms and the monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms for R ² include the monovalent hydrocarbon groups having 1 to 20 carbon atoms exemplified for R ¹ and monovalent halogenated hydrocarbon groups having 1 to 20 carbon atoms. R ² is a monovalent hydrocarbon group having 1 to 20 carbon atoms or a monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms, a portion of which is substituted with at least one selected from an oxygen atom and a sulfur atom. Specific examples include groups in which some or all of the hydrogen atoms of the hydrocarbon group or halogenated hydrocarbon group are substituted with an ester group or a sulfonyl group.

As R ² , a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms is preferable from the viewpoint of synthesizing the polymer (B) with good polymerization reactivity.
When both A ¹ and A ² are -N(R ² )-, the two R ² may be the same or different.

The divalent organic group represented by X preferably contains a group represented by the following formula (2-1).

〔式（２－１）中、Ａｒ₁及びＡｒ₂はそれぞれ独立して、置換若しくは非置換の芳香族炭化水素基である。Ｌは、単結合、－Ｏ－、－Ｓ－、－Ｎ（Ｒ⁸）－、－Ｃ（Ｏ）－、－Ｃ（Ｏ）－Ｏ－、－Ｃ（Ｏ）－ＮＨ－、－Ｓ（Ｏ）－、－Ｓ（Ｏ）₂－、－Ｐ（Ｏ）－、又は、２価の有機基である［Ｒ⁸は、水素原子、炭素数１～２０の１価の炭化水素基、又は、炭素数１～２０の１価のハロゲン化炭化水素基である。］。ｙは、０～５の整数である。ｙが２以上の場合、複数のＬは、それぞれ同一であっても異なっていてもよい。Ｒ⁶及びＲ⁷はそれぞれ独立して、単結合、メチレン基、又は、炭素数２～４のアルキレン基である。〕

[In formula (2-1), Ar ₁ and Ar ₂ are each independently a substituted or unsubstituted aromatic hydrocarbon group. L is a single bond, -O-, -S-, -N(R ⁸ )-, -C(O)-, -C(O)-O-, -C(O)-NH-, -S( O)-, -S(O) ₂ -, -P(O)-, or a divalent organic group [R ⁸ is a hydrogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, or , is a monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms. ]. y is an integer from 0 to 5; When y is 2 or more, a plurality of L's may be the same or different. R ⁶ and R ⁷ are each independently a single bond, a methylene group, or an alkylene group having 2 to 4 carbon atoms. ]

The aromatic hydrocarbon groups represented by Ar ₁ and Ar ₂ are each independently preferably an aromatic hydrocarbon group having 6 to 30 carbon atoms, and any one of a phenyl group, a naphthyl group and an anthryl group. is more preferred, and a phenyl group or a naphthyl group is particularly preferred.

Also, the aromatic hydrocarbon groups represented by Ar ₁ and Ar ₂ may each have 1 to 8 substituents. From the viewpoint of being able to synthesize the polymer (B) with good polymerization reactivity, the number of substituents possessed by the aromatic hydrocarbon groups represented by Ar ₁ and Ar ₂ is preferably 0 to 8, more preferably 0. to 4, more preferably 0 to 2.

Although the substituent is not particularly limited, for example, a halogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, a monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms , an alkylthio group having 1 to 20 carbon atoms, a nitro group, a cyano group, a carboxy group, a sulfonic acid group, a phosphonic acid group, a phosphoric acid group, a hydroxy group, a primary to tertiary amino group, a salt of a carboxy group, a sulfonic acid group salts, salts of phosphonic acid groups, salts of phosphoric acid groups, salts of hydroxy groups, and salts of primary to tertiary amino groups.

Halogen atoms include, for example, fluorine, chlorine, bromine and iodine atoms.

The monovalent hydrocarbon group having 1 to 20 carbon atoms includes, for example, the monovalent hydrocarbon groups having 1 to 20 carbon atoms exemplified as the group represented by R ¹ .

Examples of the monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms include the monovalent halogenated hydrocarbon groups having 1 to 20 carbon atoms exemplified as the group represented by R ¹ above.

Examples of alkoxy groups having 1 to 20 carbon atoms include methoxy, ethoxy, n-propoxy, isopropoxy, butoxy, pentyloxy, hexyloxy and octyloxy groups.

Examples of alkylthio groups having 1 to 20 carbon atoms include methylthio, ethylthio, n-propylthio, isopropylthio, butylthio, pentylthio, hexylthio and octylthio groups.

The substituent (R) in the secondary amino group (--NHR) and the tertiary amino group (--NR ₂ ) is not particularly limited, but is, for example, one having 1 to 20 carbon atoms exemplified as the group represented by R ¹ valent hydrocarbon groups.

There are no particular limitations on the cations that constitute the cation sites in salts of carboxy groups, salts of sulfonic acid groups, salts of phosphonic acid groups, salts of phosphoric acid groups, salts of hydroxy groups, and salts of primary to tertiary amino groups. Known cations such as Na ⁺ can be mentioned.

Substituents for the aromatic hydrocarbon groups in Ar ₁ and Ar ₂ include a halogen atom and a monovalent hydrocarbon group having 1 to 3 carbon atoms from the viewpoint of synthesizing the polymer (B) with good polymerization reactivity. , a monovalent halogenated hydrocarbon group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, an alkylthio group having 1 to 3 carbon atoms, a nitro group, a cyano group, a carboxy group, a sulfonic acid group, a phosphonic acid group , a phosphate group, a hydroxy group, a primary to tertiary amino group, a salt of a carboxy group, a salt of a sulfonic acid group, a salt of a phosphonic acid group, a salt of a phosphate group, a salt of a hydroxy group, or a primary to tertiary amino group Fluorine atom, chlorine atom, methyl group, ethyl group, fluoromethyl group, methoxy group, methylthio group, nitro group, cyano group, carboxy group, sulfonic acid group, phosphonic acid group, phosphoric acid group, hydroxy group , salts of primary to tertiary amino groups, carboxyl groups, salts of sulfonic acid groups, salts of phosphonic acid groups, salts of phosphoric acid groups, salts of hydroxyl groups, or salts of primary to tertiary amino groups are more preferred.

The divalent organic group for L is preferably a divalent organic group having 1 to 20 carbon atoms, such as a methylene group, an alkylene group having 2 to 20 carbon atoms, a halogenated methylene group, and a halogen having 2 to 20 carbon atoms. alkylene groups and divalent cardo structures.

Examples of the alkylene group having 2 to 20 carbon atoms in L include ethylene group, n-propylene group, isopropylene group, n-butylene group, sec-butylene group, neopentylene group, 4-methyl-pentane-2,2- diyl group, nonane-1,9-diyl group, and decane-1,1-diyl group.

Examples of the halogenated methylene group for L include groups in which part or all of the hydrogen atoms in a methylene group are substituted with halogen atoms such as fluorine, chlorine, bromine and iodine atoms.

As the halogenated alkylene group having 2 to 20 carbon atoms in L, for example, some or all of the hydrogen atoms of the alkylene group having 2 to 20 carbon atoms are substituted with halogen atoms such as fluorine, chlorine, bromine and iodine atoms. A group substituted with is exemplified.

The divalent cardo structure in L includes, for example, a divalent group derived from fluorene (i.e., a group from which two hydrogen atoms are removed from fluorene), a divalent group derived from phenolphthalein (i.e., phenolphthalein a group obtained by removing two hydrogen atoms from rhein), and a group represented by the following formula (L1). In the divalent group derived from fluorene and the divalent group derived from phenolphthalein, some or all of the hydrogen atoms are substituted with a monovalent chain hydrocarbon group having 1 to 20 carbon atoms. Furthermore, some or all of the hydrogen atoms including the substituent may be substituted with fluorine atoms.

〔式（Ｌ１）中、Ｒ^cは、環員数５～３０の２価の脂環式炭化水素基である。〕

[In the formula (L1), R ^c is a divalent alicyclic hydrocarbon group having 5 to 30 ring members. ]

The divalent alicyclic hydrocarbon group with 5 to 30 ring members represented by R ^c includes, for example, a monocyclic alicyclic hydrocarbon group with 5 to 15 ring members and a monocyclic ring with 5 to 15 ring members. , polycyclic alicyclic hydrocarbon groups having 7 to 30 ring members, and fluorinated alicyclic hydrocarbon groups having 7 to 30 ring members.

Examples of the monocyclic alicyclic hydrocarbon group having 5 to 15 ring members include cyclopentane-1,1-diyl group, cyclohexane-1,1-diyl group, 3,3,5-trimethylcyclohexane-1 ,1-diyl group, cyclopentene-3,3-diyl group, cyclohexene-3,3-diyl group, cyclooctane-1,1-diyl group, cyclodecane-1,1-diyl group, cyclododecane-1,1- Examples include diyl groups and groups in which some or all of the hydrogen atoms of these groups are substituted with monovalent chain hydrocarbon groups having 1 to 20 carbon atoms.

As the monocyclic fluorinated alicyclic hydrocarbon group having 5 to 15 ring members, for example, a part of the hydrogen atoms of the group exemplified as the monocyclic alicyclic hydrocarbon group having 5 to 15 ring members, or Groups entirely substituted with fluorine atoms are included.

Examples of the polycyclic alicyclic hydrocarbon group having 7 to 30 ring members include norbornane, norbornene, adamantane, tricyclo[5.2.1.0 ^2,6 ]decane, tricyclo[5.2.1. 0 ^2,6 ]heptane, pinane, camphane, decalin, nortricyclane, perhydroanthracene, perhydroazulene, cyclopentanohydrophenanthrene, bicyclo[2.2.2]-2-octene, and other polycyclic alicyclic A group other than two hydrogen atoms bonded to one carbon atom of a cyclic hydrocarbon, or a monovalent chain hydrocarbon group in which some or all of the hydrogen atoms in these groups have 1 to 20 carbon atoms Substituted groups are included.

As the polycyclic fluorinated alicyclic hydrocarbon group having 7 to 30 ring members, for example, a part of the hydrogen atoms of the group exemplified as the polycyclic alicyclic hydrocarbon group having 7 to 30 ring members, or Groups entirely substituted with fluorine atoms are included.

From the viewpoint of the structural stability of the polymer (B), L is a single bond, —O—, —S—, —C(O)—, —S(O)—, —S(O) ₂ —, —C(O)—NH—, —C(O)—O—, a methylene group, an alkylene group having 2 to 5 carbon atoms, a halogenated methylene group, a halogenated alkylene group having 2 to 10 carbon atoms, or a divalent A cardo structure is preferred. From the same point of view, y is preferably 0 to 4, more preferably 0 to 3.

Examples of the alkylene group having 2 to 4 carbon atoms for R ⁶ and R ⁷ include ethylene group, n-propylene group, isopropylene group, n-butylene group, sec-butylene group and tert-butylene group. R ⁶ and R ⁷ are each independently preferably a single bond, a methylene group, or an ethylene group from the viewpoint of synthesizing the polymer (B) with good polymerization reactivity.

Examples of monomers that are raw materials for the repeating units represented by the above formulas (1-1) to (1-3) (monomers that are raw materials for the portion containing X) include hydroquinone, resorcinol, catechol, Dihydroxyphenyl compounds such as phenylhydroquinone; 9,9-bis(4-hydroxyphenyl)fluorene, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, 9,9-bis(4-hydroxy-3- phenylphenyl)fluorene, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, bis(4-hydroxyphenyl)diphenylmethane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis( 4-hydroxy-3-methylphenyl)propane, 2,2-bis(4-hydroxy-3-phenylphenyl)propane, 4,4'-(1,3-dimethylbutylidene)bisphenol, 1,1-bis( 4-hydroxyphenyl)-nonane, 1,1-bis(4-hydroxyphenyl)-decane, bis(4-hydroxyphenyl)sulfone, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis( 4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 1,4-bis[2-(4-hydroxyphenyl)-2-propyl]benzene, 1,3-bis[2-(4-hydroxyphenyl) -Bisphenol compounds such as 2-propyl]benzene. In addition, these monomers may be used individually by 1 type, and may use 2 or more types.

The polymer (B) is usually in addition to at least one repeating unit among the repeating units represented by the above formulas (1-1), (1-2) and (1-3), and if necessary other or a terminal structure. Therefore, at least one repeating unit among the repeating units represented by the formulas (1-1), (1-2) and (1-3) is bound to each other, or the other structure Binds to units and terminal structures.

Examples of monomers from which other structural units are derived include structural units containing carbonate bonds, thiocarbonate bonds, or selenocarbonate bonds such as diphenyl carbonate, diphenylthiocarbonate, diphenylselenocarbonate, phosgene, thiophosgene, and selenophosgene. Inducing compounds; dihydroxy compounds such as benzenedimethanol and cyclohexanedimethanol; phosphine oxide compounds such as bis(fluorophenyl)phenylphosphine oxide, bis(fluorophenyl)naphthylphosphine oxide and bis(fluorophenyl)anthrylphosphine oxide; Dihalides of dicarboxylic acids such as acid dichloride, isophthalic acid dichloride, terephthalic acid dichloride and the like can be mentioned. In addition, these monomers may be used individually by 1 type, and may use 2 or more types.

As the terminal structure, a structure derived from a monomer that is a raw material of the repeating unit represented by the formulas (1-1) to (1-3), a structure derived from a monomer that induces the other structural unit , or a structure derived from a desired terminal blocking agent.

The content of the repeating units represented by the formulas (1-1), (1-2) and (1-3) in the polymer (B) is 100 in total of all repeating units in the polymer (B). It is preferably 1 to 95 mol %, more preferably 5 to 80 mol % based on mol %.

A method for synthesizing the polymer (B) is not particularly limited, and a known method can be used. For example, the above formulas (1-1), (1-2) and (1-3) monomers as starting materials for the repeating units and, if necessary, the other structural unit-inducing unit It can be synthesized by heating the polymer and the terminal blocking agent together with an alkali metal, an alkali metal compound, or the like in an organic solvent.

The lower limit of the weight average molecular weight (Mw) of the polymer (B) is preferably 500, more preferably 1,000, even more preferably 2,000, and particularly preferably 3,000. The upper limit of Mw is preferably 600,000, more preferably 300,000, still more preferably 200,000.

The lower limit of the glass transition temperature (Tg) of the polymer (B) is preferably 70°C, more preferably 80°C, and the upper limit is preferably 320°C, more preferably 300°C from the viewpoint of workability. .

Examples of these polymers (B) include, for example, the polymers described in JP-A-2015-209511, WO 2016/143447, JP-A-2017-197725, JP-A-2018-024827, and the like. can.

The content of the polymer (B) is 100% by mass of the solids constituting the present material (e.g. 100% by mass of the solids in the present composition; the total solid content of the magnetic powder (A) and the coating layer in the present filler) 100% by mass), preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and preferably 40% by mass or less, more preferably 20% by mass or less.
When the content of the polymer (B) is within the above range, it is possible to easily form an insulating layer that has a high magnetic permeability, a small loss factor, and excellent insulating reliability, especially in the frequency range of 1 MHz to 1 GHz. can.

<Curable compound (C)>
The curable compound (C) (hereinafter also referred to as “compound (C)”) is a compound that is cured by irradiation with heat or light (e.g., visible light, ultraviolet light, near-infrared rays, far-infrared rays, electron beams), which will be described later. It may require a curing aid (D) for curing. Examples of such compounds (C) include epoxy compounds, cyanate ester compounds, vinyl compounds, silicone compounds, oxazine compounds, maleimide compounds, allyl compounds, acrylic compounds, methacrylic compounds, urethane compounds, oxetane compounds, methylol compounds, and and propargyl compounds. Among these, epoxy compounds, cyanate ester compounds, vinyl compounds, silicone compounds, oxazine compounds, maleimide compounds, allyl compounds, and oxetanes are particularly preferred from the viewpoint of compatibility with the polymer (B) and properties such as heat resistance. It is preferably at least one of a compound, a methylol compound, and a propargyl compound.
Compound (C) may be used alone or in combination of two or more.

Examples of the epoxy compound include compounds represented by the following formulas (c1-1) to (c1-6). The compound represented by the following formula (c1-6) is epoxy group-containing NBR particles "XER-81" manufactured by JSR Corporation.
Examples of the epoxy compound further include polyglycidyl ether of dicyclopentadiene-phenol polymer, phenol novolac type liquid epoxy compound, cresol novolak type epoxy compound, epoxidized styrene-butadiene block copolymer, and 3',4'-epoxy. Cyclohexylmethyl-3,4-epoxycyclohexane carboxylate and the like are also included.

［式（ｃ１－５）中、ｎは０～５０００であり、ｍは独立して、０～５０００である。］

[In the formula (c1-5), n is 0 to 5000, and m is independently 0 to 5000. ]

Examples of the cyanate ester compounds include compounds represented by the following formulas (c2-1) to (c2-7).

［式（ｃ２－６）及び（ｃ２－７）中、ｎは独立して、０～３０である。］

[In formulas (c2-6) and (c2-7), n is independently 0 to 30. ]

Examples of the vinyl compound include compounds represented by the following formulas (c3-1) to (c3-5).

［式（ｃ３－４）中、ｎは１～５０００である。］

[In the formula (c3-4), n is 1 to 5000. ]

Examples of the silicone compound include compounds represented by the following formulas (c4-1) to (c4-16). As R in formula (c4-1), one of the following is selected, and when a group having an acryloyl group is selected, it can be treated as the acrylic compound, and a group having a methacryloyl group is selected. When a group having an oxetane group is selected, it can be treated as the oxetane compound. In formulas (c4-2) to (c4-16), each R is independently an organic group selected from an alkyl group, an alicyclic saturated hydrocarbon group, an aryl group, and an alkenyl group, and n is It is an integer from 0 to 1000 (preferably an integer from 0 to 100). Examples of the alkyl group, the alicyclic saturated hydrocarbon group, the aryl group, and the alkenyl group include groups similar to those exemplified in the description of R ¹ in formula (1). .

Examples of the oxazine compound include compounds represented by the following formulas (c5-1) to (c5-5).

Examples of the maleimide compound include compounds represented by the following formulas (c6-1) to (c6-5).

［式（ｃ６－２）中、Ｅｔはエチル基であり、式（ｃ６－３）中、ｎは０～３０である。］

[In the formula (c6-2), Et is an ethyl group, and in the formula (c6-3), n is 0 to 30. ]

Examples of the allyl compound include compounds represented by the following formulas (c7-1) to (c7-6). In particular, the allyl compound is preferably a compound having two or more (especially 2 to 6, further 2 to 3) allyl groups.

Examples of the oxetane compound include compounds represented by the following formulas (c8-1) to (c8-3).

［式（ｃ８－１）及び（ｃ８－２）中、括弧で括った繰り返し単位の繰り返し単位数はそれぞれ独立に、０～３０である。］

[In the formulas (c8-1) and (c8-2), the number of repeating units in parenthesized repeating units is independently 0 to 30. ]

Examples of the methylol compound include methylol compounds described in JP-A-2006-178059 and JP-A-2012-226297. Specifically, for example, melamine-based methylol compounds such as polymethylolated melamine, hexamethoxymethylmelamine, hexaethoxymethylmelamine, hexapropoxymethylmelamine, hexabutoxymethylmelamine; polymethylolated glycoluril, tetramethoxymethylglycoluril, glycoluril-based methylol compounds such as tetrabutoxymethylglycoluril; 3,9-bis[2-(3,5-diamino-2,4,6-triazaphenyl)ethyl]-2,4,8,10-tetra Oxospiro[5.5]undecane, 3,9-bis[2-(3,5-diamino-2,4,6-triazaphenyl)propyl]-2,4,8,10-tetraoxospiro[5 5] Compounds obtained by methylolating guanamine such as undecane, and guanamine-based methylol compounds such as compounds obtained by alkyl-etherifying all or part of the active methylol groups in the compound.

Examples of the propargyl compound include compounds represented by the following formulas (c9-1) to (c9-2).

The content of the compound (C) is 100% by mass of the solids constituting the present material (e.g., 100% by mass of the solids in the present composition; the total solid content of the magnetic powder (A) and the coating layer in the present filler is 100% by mass). % by mass), preferably 0.1% by mass or more, more preferably 0.2% by mass or more, still more preferably 0.5% by mass or more, preferably 40% by mass or less, more preferably 30% by mass % or less, more preferably 20 mass % or less.
When the content of the compound (C) is within the above range, it is preferable from the viewpoint that the toughness, heat resistance, and chemical resistance of the cured product of the present material can be further improved.

Further, when the total of the compound (C) and the polymer (B) is 100% by mass, the content of the compound (C) is preferably 1% by mass or more, more preferably 5% by mass or more, and even more preferably It is 10% by mass or more, preferably 99% by mass or less, more preferably 95% by mass or less, and even more preferably 90% by mass or less.
When the content of the compound (C) is within the above range, it is preferable from the viewpoint that the toughness, heat resistance, and chemical resistance of the cured product of the present material can be further improved.

<Curing aid (D)>
Examples of the curing aid (D) include curing agents, thermal reaction initiators (thermal radical generators, thermal acid generators, thermal base generators), photoreaction initiators (photoradical generators, photoacid generators, polymerization initiators such as photobase generators).
The curing aid (D) may be used singly or in combination of two or more.

Examples of the curing aid (D) when an epoxy compound is used as the compound (C) include amine-based curing agents, acid-based or acid-anhydride-based curing agents, basic active hydrogen compounds, imidazoles, and polymercaptan-based curing agents. curing agents such as phenolic resins, urea resins, melamine resins, isocyanate-based curing agents, and Lewis acids.

Examples of the amine curing agent include ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, hexamethylenediamine, iminobispropylamine, bis(hexamethylene)triamine, 1,3,6-trisaminomethylhexane, and the like. of polyamines; mencenediamine (MDA), isophoronediamine (IPDA), bis(4-amino-3-methylcyclohexyl)methane, diaminodicyclohexylmethane, bisaminomethylcyclohexane, 3,9-bis(3-aminopropyl)- Cycloaliphatic polyamines such as 2,4,8,10-tetraoxaspiro[5.5]undecane, norbornane skeleton diamines represented by NBDA manufactured by Mitsui Chemicals, Inc.; Aliphatic polyamines containing aromatic rings; aromatic polyamines such as metaphenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, diaminodiethyldiphenylmethane, and derivatives thereof.

Furthermore, other amine-based curing agents include, for example, Mannich-modified amines obtained by reacting polyamines with aldehydes and/or phenols; amine adducts (polyamine epoxy resin adducts), polyamine-ethylene oxide adducts, polyamine-propylene oxide adducts. , cyanoethylated polyamines, ketimines which are reaction products of aliphatic polyamines and ketones; tetramethylguanidine, triethanolamine, piperidine, pyridine, benzyldimethylamine, picoline, 2-(dimethylaminomethyl)phenol, dimethylcyclohexylamine, dimethyl benzylamine, dimethylhexylamine, dimethylaminophenol, dimethylamino-p-cresol, N,N'-dimethylpiperazine, 1,4-diazabicyclo[2.2.2]octane, 2,4,6-tris(dimethylamino secondary or tertiary amines such as methyl)phenol and 1,8-diazabicyclo[5.4.0]-7-undecene; reacting dimer acid with polyamines such as diethylenetriamine and triethylenetetramine; A liquid polyamide consisting of

Examples of the acid-based or acid anhydride-based curing agent include polycarboxylic acids such as adipic acid, azelaic acid and decanedicarboxylic acid; phthalic anhydride, trimellitic anhydride, ethylene glycol bis(anhydrotrimeltate); Aromatic acid anhydrides such as glycerol tris (anhydrotrimellitate), pyromellitic anhydride, 3,3′,4,4′-benzophenonetetracarboxylic anhydride; maleic anhydride, succinic anhydride, tetrahydrophthalic anhydride Acid, methyltetrahydrophthalic anhydride, methylnadic anhydride, alkenylsuccinic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylcyclohexenetetracarboxylic anhydride, methylhimic anhydride, trialkyltetrahydrophthalic anhydride , Poly(phenylhexadecanedioic acid) anhydride and other cyclic aliphatic acid anhydrides; and halogenated acid anhydrides such as chlorendic anhydride and tetrabromophthalic anhydride.

Examples of the basic active hydrogen compound include dicyandiamide and organic acid dihydrazide.

Examples of the imidazoles include 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 1-benzyl-2-methylimidazole, 1- Cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 2-methylimidazolium isocyanurate, 2,4-diamino-6-[2-methylimidazoline-(1)]-ethyl-S -triazine, 2,4-diamino-6-[2-ethyl-4-methylimidazoline-(1)]-ethyl-S-triazine.

Examples of the polymercaptan curing agent include partial epoxy adducts of 2,2′-bismercaptoethyl ether; pentaerythritol tetrathioglycolate, dipentaerythritol hexathioglycolate, trimethylolpropane tristhioglycolate, and the like. Esters of thioglycolic acid; Compounds containing a mercapto group such as polysulfide rubber having a mercapto group at the end.

Examples of the isocyanate-based curing agent include isocyanate compounds such as toluene diisocyanate, hexamethylene diisocyanate, and xylene diisocyanate; and blocked isocyanate compounds obtained by masking isocyanate groups by reacting them with blocking agents such as phenol, alcohol, and caprolactam. mentioned.

Examples of the Lewis acid include diaryliodonium salts and triarylsulfonium salts.

In addition, when an epoxy compound is used as the compound (C), the curing aid (D) includes an onium salt compound, a sulfone compound, a sulfonic acid ester compound, a sulfonimide compound, a disulfonyldiazomethane compound, a disulfonylmethane compound, and an oxime sulfonate. In addition to compounds, hydrazinesulfonate compounds, triazine compounds and nitrobenzyl compounds, photoacid generators such as organic halides and disulfones can also be used.

Furthermore, as the curing aid (D) when an epoxy compound is used as the compound (C), (Z)-{[bis(dimethylamino)methylidene]amino}-N-cyclohexyl(cyclohexylamino)methaniminium=tetrakis (3-fluorophenyl)borate, 1,2-dicyclohexyl-4,4,5,5-tetramethylbiguanidinium=n-butyltriphenylborate, 9-anthrylmethyl=N,N-diethylcarbamate, (E )-1-[3-(2-hydroxyphenyl)-2-propenoyl]piperidine, 1-(anthraquinon-2-yl)ethyl imidazole carboxylate, 2-nitrophenylmethyl-4-methacryloyloxypiperidine-1-carboxy photobase generators such as phosphate, 1,2-diisopropyl-3-[bis(dimethylamino)methylene]guanidinium 2-(3-benzoylphenyl)propionate, and the like can also be used.

Examples of the curing aid (D) when a cyanate ester compound is used as the compound (C) include zinc octylate, zinc naphthenate, cobalt naphthenate, copper naphthenate, iron acetylacetonate, nickel octylate, manganese octylate, and the like. organic metal salts of phenol, xylenol, cresol, resorcinol, catechol, octylphenol, phenol compounds such as nonylphenol, alcohols such as 1-butanol and 2-ethylhexanol, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2- Imidazoles such as phenyl-4-methyl-5-hydroxymethylimidazole and derivatives such as adducts of carboxylic acids or acid anhydrides of these imidazoles, benzyldimethylamine, 4-methyl-N,N-dimethylbenzylamine Phosphorus compounds such as amines, phosphine-based compounds, and phosphine oxide-based compounds can be used.
Furthermore, the photoacid generator and photobase generator explained as the curing aid (D) in the case of using the epoxy compound can also be used.

Examples of the curing aid (D) when a vinyl compound is used as the compound (C) include compounds (polymerizing agents) that generate cationic or radical active species by heat or light. Cationic polymerization agents include, for example, diaryliodonium salts and triarylsulfonium salts. Examples of radical polymerization agents include benzoin-based compounds such as benzoinacetophenone, acetophenone-based compounds such as 2,2-dimethoxy-2-phenylacetophenone, sulfur-based compounds such as 2,4-diethylthioxanthone, and azobisisobutyronitrile. and azo compounds such as 2,5-dimethyl-2,5-di(t-butylperoxy)hexane and organic peroxides such as dicumyl peroxide.

Examples of the curing aid (D) when a vinyl compound is used as the compound (C) include acetophenone, propiophenone, benzophenone, xanthol, benzaldehyde, anthraquinone, triphenylamine, carbazole, 3-methylacetophenone, 4-methylacetophenone, 3-pentylacetophenone, 4-methoxyacetophenone, 3-bromoacetophenone, 4-allylactophenone, p-diacetylbenzene, 3-methoxybenzophenone, 4-methylbenzophenone, 4-chlorobenzophenone, 4,4' -dimethoxybenzophenone, 4-chloro-4'-benzylbenzophenone, 3-chloroxanthone, 3,9-dichloroxanthone, 3-chloro-8-nonylxanthone, benzoin, benzoin methyl ether, benzoin butyl ether, bis(4-dimethylamino Photoradical generators such as phenyl)ketone, benzylmethoxyketal, and 2-chlorothioxanthone can also be used.

Examples of the curing aid (D) when a silicone compound is used as the compound (C) include platinum black, platinum chloride, chloroplatinic acid, a reaction product of chloroplatinic acid and a monohydric alcohol, chloroplatinic acid and Complexes with olefins, platinum-based catalysts such as platinum bisacetoacetate; platinum-group metal catalysts such as palladium-based catalysts; rhodium-based catalysts; zinc benzoate and zinc octylate can be used.

Examples of the curing aid (D) when a silicone compound is used as the compound (C) include acetophenone, propiophenone, benzophenone, xanthol, benzaldehyde, anthraquinone, triphenylamine, carbazole, 3-methylacetophenone, 4-methylacetophenone, 3-pentylacetophenone, 4-methoxyacetophenone, 3-bromoacetophenone, 4-allylactophenone, p-diacetylbenzene, 3-methoxybenzophenone, 4-methylbenzophenone, 4-chlorobenzophenone, 4,4'- Dimethoxybenzophenone, 2,2'-diethoxyacetophenone, 4-chloro-4'-benzylbenzophenone, 3-chloroxanthone, 3,9-dichloroxanthone, 3-chloro-8-nonylxanthone, benzoin, benzoin methyl ether, benzoin Butyl ether, bis(4-dimethylaminophenyl)ketone, benzylmethoxyketal, 2-chlorothioxanthone, diethylacetophenone, 1-hydroxycyclohexylphenylketone, 2-methyl-1-{4-(methylthio)phenyl}-2-morpholino- 1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1-one, 1-{4-(2-hydroxyethoxy)-phenyl}-2-methyl-1-propane Photoinitiators such as -1-one, 2,2-dimethoxy-2-phenylacetophenone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, cyclohexylphenylketone and the like can also be used.

Examples of the curing aid (D) when an oxazine compound is used as the compound (C) include phenol and its derivatives, cyanate esters, Bronsted acids such as p-toluenesulfonic acid, adipic acid, and p-toluenesulfonic acid. Curing agents such as esters, 4,4'-diaminodiphenylsulfone, aromatic amine compounds such as melamine, bases such as 2-ethyl-4-methylimidazole, boron trifluoride, and Lewis acids can be used.
Furthermore, the photoacid generator and photobase generator explained as the curing aid (D) in the case of using the epoxy compound can also be used.

Examples of the curing aid (D) when a maleimide compound is used as the compound (C) include imidazole, 1-methylimidazole, 1-benzyl-2-methylimidazole, 2-methylimidazoline, N,N-diisopropylethylamine, Bases such as 1,4-dimethylpiperazine, quinoline, triazole, benzotriazole, and DBU, phosphorus compounds such as triphenylphosphine, and curing agents such as azobisisobutyronitrile can be used.
Furthermore, the photoacid generator and photobase generator explained as the curing aid (D) in the case of using the epoxy compound can also be used.

Examples of the curing aid (D) when an allyl compound or propargyl compound is used as the compound (C) include azo initiators such as azobisisobutyronitrile and dimethyl 2,2′-azobisisobutyrate, ketone peroxides, Peroxyketals, hydroperoxides, dialkyl peroxides, diacyl peroxides, peroxydicarbonates, peroxides such as peroxyesters, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropane- Acetophenones such as 1,1′-hydroxycyclohexylphenyl ketone, benzoin such as benzoin and benzoin ethyl ether, benzophenones such as benzophenone, phosphorus such as acylphosphine oxide, sulfur such as thioxanthone, benzyl, 9,10- Benzyl-based curing agents such as phenanthrenequinone, and peroxycarbonate-based curing agents can be used.
Furthermore, the photoacid generator and photobase generator explained as the curing aid (D) in the case of using the epoxy compound can also be used.

As the curing aid (D) in the case of using an oxetane compound or a methylol compound as the compound (C), for example, a photo- or thermal cation generator can be used.

Examples of photocation generators include onium salt compounds, halogen-containing compounds, sulfone compounds, sulfonic acid compounds, sulfonimide compounds, and diazomethane compounds.
Specific examples of the onium salt compound, halogen-containing compound, sulfone compound, sulfonic acid compound, sulfonimide compound and diazomethane compound are described in paragraphs [0074] to [0079] of JP-A-2014-186300. compound.

Specific examples of halogen-containing compounds include haloalkyl group-containing hydrocarbon compounds and haloalkyl group-containing heterocyclic compounds. Specific examples of preferred halogen-containing compounds include 1,10-dibromo-n-decane, 1,1-bis(4-chlorophenyl)-2,2,2-trichloroethane; phenyl-bis(trichloromethyl)-s-triazine , 4-methoxyphenyl-bis(trichloromethyl)-s-triazine, styryl-bis(trichloromethyl)-s-triazine, naphthyl-bis(trichloromethyl)-s-triazine, 2-[2-(5-methylfuran -2-yl)ethenyl]-4,6-bis-(trichloromethyl)-1,3,5-triazine and other s-triazine derivatives.

Examples of the thermal cation generator include benzyl(4-hydroxyphenyl)(methyl)sulfonium=tetrakis(pentafluorophenyl)borate, (4-hydroxyphenyl)(dimethyl)sulfonium=tetrakis(pentafluorophenyl)borate, 4 -acetoxyphenyl(dimethyl)sulfonium = tetrakis(pentafluorophenyl)borate, (4-hydroxyphenyl)methyl(4-methylbenzyl)sulfonium = tetrakis(pentafluorophenyl)borate, benzyl(4-hydroxyphenyl)(methyl)sulfonium = hexafluorophosphate.

When the curing aid (D) is contained, the content of the curing aid (D) is within the range in which the present material, specifically the present composition or coating layer, can be cured satisfactorily to obtain a cured product. Preferably. Specifically, the content of the curing aid (D) is preferably 0.1 parts by mass or more, more preferably 1 part by mass, with respect to a total of 100 parts by mass of the polymer (B) and the compound (C). or more, preferably 20 parts by mass or less, more preferably 10 parts by mass or less.

<Other ingredients>
The present material, specifically the present composition or coating layer, may further contain other components within a range that does not impair the effects of the present invention.
Such other components include, for example, antioxidants, reinforcing agents, lubricants, flame retardants, antibacterial agents, colorants, release agents, foaming agents, and polymers other than polymer (B) (e.g., epoxy resin , polyimide, polyarylene, and other known polymers having low dielectric constant and low dielectric loss tangent characteristics).
Each of these other components may be used alone or in combination of two or more.

In addition, since this material has the polymer (B), it is excellent in flame retardancy. Therefore, in order to obtain the present material with low environmental load, it is preferable not to contain the flame retardant.

Examples of the antioxidant include hindered phenol-based compounds, phosphorus-based compounds, sulfur-based compounds, metal-based compounds, and hindered amine-based compounds. Among these, hindered phenol compounds are preferred.

A compound having a molecular weight of 500 or more is preferable as the hindered phenol compound. Hindered phenolic compounds having a molecular weight of 500 or more include, for example, triethylene glycol-bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol-bis[ 3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2,4-bis-(n-octylthio)-6-(4-hydroxy-3,5-di-t-butylanilino) -3,5-triazine, pentaerythritol tetrakis[3-(3,5-t-butyl-4-hydroxyphenyl)propionate], 1,1,3-tris[2-methyl-4-[3-(3, 5-di-t-butyl-4-hydroxyphenyl)propionyloxy]-5-t-butylphenyl]butane, 2,2-thio-diethylenebis[3-(3,5-di-t-butyl-4- hydroxyphenyl)propionate], octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, N,N-hexamethylenebis(3,5-di-t-butyl-4-hydroxy- hydrocinnamamide), 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, tris-(3,5-di-t- Butyl-4-hydroxybenzyl)-isocyanurate, 3,9-bis[2-[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1-dimethylethyl]- 2,4,8,10-tetraoxaspiro[5.5]undecane.

When the present material, specifically, the present composition or coating layer contains an antioxidant, the content of the antioxidant is, for example, a total of 100 parts by mass of the polymer (B) and the compound (C). On the other hand, it is preferably 0.01 parts by mass or more and 10 parts by mass or less.

1-1. Present Filler As described above, a preferred embodiment of the present material is a magnetic filler ( This is the main filler).
The coating layer may contain the compound (C), the curing aid (D) and other components in addition to the polymer (B).

The mass ratio of the magnetic powder (A) to the coating layer (mass of the magnetic powder (A)/mass of the coating layer) in the present filler is preferably 1 or more, more preferably 1.5 or more, and still more preferably 2 or more. It is preferably 100 or less, more preferably 75 or less, still more preferably 50 or less.
By setting the mass ratio of the magnetic powder (A) to the coating layer within the above range, it is possible to easily obtain a filler in which the coating layer and the magnetic powder (A) are less likely to separate.
The mass of the magnetic powder (A) in the above mass ratio represents the amount of the magnetic powder (A) charged in the production of the magnetic filler, and the mass of the coating layer represents the amount of the coating layer in the production of the magnetic filler. It represents the total charged amount of the polymer (B) to be formed, the compound (C) and the curing aid (D).

The coating layer of this filler is preferably in the state of a B-stage resin layer. By being in the state of the B-stage resin layer, the adhesiveness between the filler is excellent (the adhesiveness is exhibited by hot pressing, etc. at the time of processing and molding), and the molded article such as a magnetic member (e.g., magnetic sheet) can be formed from the filler. A tough member (eg, sheet) can be easily formed when forming the.
In this specification, the term "B-stage resin layer" refers to a layer in which the resin is semi-cured. Whether or not the resin layer is a B-stage resin layer can be confirmed by measuring the amount of heat generated by the resin layer (the present filler) using a DSC (differential scanning calorimeter). Specifically, when the calorific value is 5 J/g or more, it can be said that the resin layer (coating layer) is in the state of a B-stage resin layer.

The thickness of the coating layer (the coating layer in the state of the B-stage resin layer) is preferably 0.005 μm or more from the viewpoint of easily obtaining a filler that does not easily separate from the magnetic powder (A). , more preferably 0.01 μm or more, still more preferably 0.015 μm or more, preferably 5 μm or less, more preferably 4 μm or less, still more preferably 3 μm or less.
When the thickness of the coating layer is within the above range, the uniformity of the film thickness can be maintained while ensuring insulation.
The thickness of the coating layer can be measured, for example, by observing the cross section of the present filler with an SEM. The average film thickness can also be calculated by measuring the amount of the coating layer-forming material used using the thermal weight loss rate obtained by TGA measurement.

The relative magnetic permeability (μ′) of the present filler in a frequency range of 1 MHz to 1 GHz is preferably 2 or more, more preferably 3 or more.
When the relative magnetic permeability is within the above range, it is easy to increase the inductance value, and it is easy to manufacture a thin film or a small inductor.
In addition, the loss factor tan δ (ratio of magnetic permeability loss μ″ to relative magnetic permeability μ′ (μ″/μ′)) of the present filler in the frequency range of 1 MHz to 1 GHz is preferably 0.2 or less, more It is preferably 0.1 or less.
When the loss factor is within the above range, iron loss can be suppressed, and heat generation can be easily suppressed.
Specifically, the relative permeability (μ′) and magnetic permeability loss (μ″) can be measured by the method described in Examples.
The relative magnetic permeability and the loss factor are characteristics when the coating layer is in a completely cured state (state of the C-stage resin layer).

The present filler is not particularly limited as long as it can form a coating layer containing the polymer (B) on the surface of the magnetic powder (A).
Methods for forming such a coating layer include, for example, a method in which magnetic powder (A) is agitated in a container, a material for forming a coating layer is sprayed to coat the magnetic powder (A), and the magnetic powder (A) is dried if necessary. ) and a coating layer-forming material by spraying and drying the mixed liquid containing the magnetic powder (A) and the coating layer-forming material, filtering the mixed liquid containing the magnetic powder (A) and the coating layer-forming material to recover the powder, and optionally A method of drying, and a method of stirring a mixed solution containing the magnetic powder (A) and the material for forming the coating layer in the presence of a supercritical fluid and, if necessary, drying.
The present filler obtained by these methods is preferably recovered without agglomeration in a solvent-dried state.

The coating layer-forming material is not particularly limited as long as it contains the polymer (B), but may contain the compound (C), the curing aid (D) and other components, and may further include a dispersion medium and It may contain a solvent. Examples of the solvent include the solvent (E) described in the section of the present composition below.

1-2. Present Composition As described above, a preferred embodiment of the present material is a magnetic composition (present composition) containing the magnetic powder (A) and the polymer (B).
The composition may be a composition containing the polymer (B) and the magnetic powder (A) that is not covered with the coating layer containing the polymer (B), or a composition containing the filler. Preferably.
The form of the present composition is not particularly limited, and examples thereof include liquid and paste.

The composition may contain the compound (C), the curing aid (D) and other components in addition to the magnetic powder (A) and the polymer (B). Furthermore, the composition may contain a solvent (E).
Further, since the polymer (B) has excellent solubility, a solventless composition can be obtained by dissolving the polymer (B) in the liquid compound (C).

・Solvent (E)
The composition may contain a solvent, if desired. Examples of the solvent include N,N-dimethylacetamide, N,N-dimethylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, and the like. Amide solvents; ester solvents such as γ-butyrolactone and butyl acetate; ketone solvents such as acetone, cyclopentanone, cyclohexanone, methyl ethyl ketone, and benzophenone; ether solvents such as 1,2-methoxyethane and diphenyl ether; -polyfunctional solvents such as 2-propanol and propylene glycol methyl ether acetate; sulfone solvents such as sulfolane, dimethylsulfoxide, diethylsulfoxide, dimethylsulfone, diethylsulfone, diisopropylsulfone and diphenylsulfone; methylene chloride, benzene, toluene, xylene , dialkoxybenzene (the number of carbon atoms in the alkoxy group; 1 to 4), and trialkoxybenzene (the number of carbon atoms in the alkoxy group; 1 to 4).
These solvents may be used individually by 1 type, and may be used 2 or more types.

The content of the solvent (E) in the present composition is not particularly limited, but is preferably 0 parts by mass or more and 2000 parts by mass or less with respect to a total of 100 parts by mass of the polymer (B) and the compound (C). , and more preferably 0 to 200 parts by mass. Further, when the solubility of the polymer (B) or the compound (C) in the solvent (E) is high, the content of the solvent (E) in the present composition is 50 parts by mass or more and 100,000 It may be less than or equal to parts by mass.

The preparation method of the present composition is not particularly limited, but for example, magnetic powder (A), polymer (B), and, if necessary, other additives (e.g., compound (C), curing aid (D ), the solvent (E), and the other components) can be uniformly mixed.

2. Magnetic Member A magnetic member according to an embodiment of the present invention is formed from this material.
The magnetic member includes a magnetic sheet, a core, a toroidal core, a member (magnetic layer) having a wound coil inside (a wound coil is embedded inside), and a member (magnetic core) filled inside an air core coil. ), an exterior material for sealing the coil, and the like. The shape of the core may be appropriately selected according to the desired application and properties. The magnetic member can also be used as an insulating layer that constitutes a substrate or an element.

<Magnetic sheet>
The magnetic sheet can be produced, for example, by filling a release-treated mold with the present filler, preferably the present filler having a B-stage resin layer, followed by die pressing.
The magnetic sheet can also be produced by molding the present composition by a known molding method such as a melt molding method or a solvent casting method.
The magnetic sheet can also be obtained as a laminate of the support and the magnetic sheet (supported magnetic sheet) by forming the magnetic sheet on the support.
In this specification, there is no particular distinction between sheets, films, membranes, and the like.

The thickness of the magnetic sheet is preferably 250 μm or less, more preferably 200 μm or less, even more preferably 150 μm or less, more preferably 100 μm or less, still more preferably 80 μm or less, and more preferably 80 μm or less, from the viewpoint of thinning the target for which the sheet is used. is 60 μm or less, particularly preferably 40 μm or less. Although the lower limit of the thickness of the magnetic sheet is not particularly limited, it is usually 5 μm or more, preferably 10 μm or more, more preferably 20 μm or more.

Examples of the support include a film made of a plastic material, a metal foil, and a release paper, and a film made of a plastic material and a metal foil are preferable.

Examples of the plastic material include polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), (meth) acrylics such as polycarbonate (PC) and polymethyl methacrylate (PMMA), cyclic polyolefins, and triacetylcellulose (TAC). ), polyether sulfide (PES), polyether ketone, and polyimide. Among them, PET and PEN are preferable, and inexpensive PET is particularly preferable.

Examples of the metal foil include copper foil and aluminum foil, with copper foil being preferred. 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 other metals (e.g., tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium) may be used. may

The support may be a support whose surface to be bonded to the magnetic sheet is subjected to surface treatment such as matte treatment or corona treatment.

Although the thickness of the support is not particularly limited, it is preferably 5 to 75 μm, more preferably 10 to 60 μm.
The support may be a release layer-attached support, and when the release layer-attached support is used, the thickness of the release layer-attached support as a whole is preferably within the above range. .

In the magnetic sheet with a support, the surface of the magnetic sheet that is not bonded to the support (that is, the surface of the magnetic sheet on the side opposite to the support) is capable of suppressing adhesion of dust and the like and scratches on the magnetic sheet. A protective film conforming to the support may be further laminated from the point of view of being able to do so. When the support-attached resin sheet has a protective film, it can be used for a desired purpose by peeling off the protective film.
Although the thickness of the protective film is not particularly limited, it is, for example, 1 to 40 μm.
The magnetic sheet, the magnetic sheet with the support, and the magnetic sheet with the support having the protective film can be wound into a roll and stored.

3. Coil A coil according to an embodiment of the present invention includes the magnetic member.
Examples of the form of the coil including the magnetic member include, for example, a form in which a core made of the magnetic member is used as a core of the coil, a form in which the magnetic member is used as a member to be filled inside an air-core coil, and the entire coil is A mode in which it is embedded in a magnetic member (magnetic layer) is exemplified. Further, the magnetic member may be used as an exterior material that seals the coil.
The shape of the coil is not particularly limited, and a known structure used for inductors is suitable. For example, there is a coil described in JP-A-2019-212664.

4. Inductor Wiring Board The inductor wiring board according to one embodiment of the present invention is not particularly limited as long as it includes an inductor element and includes the magnetic member or coil, and may have a known structure.
Examples of the magnetic member included in the inductor wiring board include a magnetic layer (having wiring).

The inductor wiring board can be manufactured by a known method. Suitable examples of the method include, for example, the method described in International Publication No. 2018/194099.

A frequency at which the inductor element included in the inductor wiring board can function is, for example, 1 MHz to 1 GHz. In addition, the inductor element included in the inductor wiring board is assumed to be a power supply system.

The inductor wiring board can be used as a wiring board for mounting electronic components such as semiconductor chips, and can also be used as a (multilayer) printed wiring board using the wiring board as an inner layer substrate. Further, the wiring board can be used as chip inductor components obtained by individualizing, and can also be used as a printed wiring board in which the chip inductor components are surface-mounted.

Further, when the printed wiring board has a cavity, it may be a printed wiring board with a built-in inductor wiring board, in which the inductor wiring board is built in the cavity. For details of the wiring board, the description in JP-A-2012-186440 can be referred to.

In addition, various types of semiconductor devices can be manufactured using the inductor wiring board. The semiconductor device can be suitably used for electrical appliances (eg computers, mobile phones, digital cameras, televisions) and vehicles (eg motorcycles, automobiles, trains, ships, aircraft) and the like.

EXAMPLES The present invention will be specifically described below based on Examples, but the present invention is not limited to these Examples. "Parts" in Examples and Comparative Examples are based on mass unless otherwise specified.

<Synthesis Example 1>
1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane (BisTMC) (18.6 g, 60.0 mmol), 4,6- Dichloropyrimidine (Pym) (8.9 g, 60.0 mmol) and potassium carbonate (11.1 g, 81.0 mmol) were weighed, N-methyl-2-pyrrolidone (64 g) was added, and the temperature was maintained at 130°C under a nitrogen atmosphere. was reacted for 6 hours. After completion of the reaction, N-methyl-2-pyrrolidone (368 g) was added, the salt was removed by filtration, and this solution was poured into methanol (9.1 kg). The precipitated solid was filtered off, washed with a small amount of methanol, filtered again and collected, dried under reduced pressure at 120 ° C. for 12 hours using a vacuum dryer, and the structure represented by the following formula (P-1) A polymer P-1 having units was obtained (yield: 20.5 g, yield: 90%, weight average molecular weight (Mw): 32,000, glass transition temperature (Tg): 206°C).

The glass transition temperature (Tg) is measured using a dynamic viscoelasticity measuring device (manufactured by Seiko Instruments Inc., "DMS7100") at a frequency of 1 Hz and a heating rate of 10 ° C./min. The temperature was set to the maximum. The loss tangent was obtained by dividing the loss modulus by the storage modulus.

Further, the weight average molecular weight (Mw) was measured using a GPC apparatus ("HLC-8320 type" manufactured by Tosoh Corporation) under the following conditions.
Column: "TSKgel α-M" manufactured by Tosoh Corporation and "TSKgel guard column α" manufactured by Tosoh Corporation connected Developing solvent: N-methyl-2-pyrrolidone Column temperature: 40 ° C.
Flow rate: 1.0 mL/min Sample concentration: 0.75% by mass
Sample injection volume: 50 μL
Detector: Differential refractometer Standard substance: Monodisperse polystyrene

<Synthesis Example 2>
1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane (BisTMC) (10.7 g, 34.5 mmol), 3,6- Dichloropyridazine (Pyd) (5.1 g, 34.2 mmol) and potassium carbonate (6.5 g, 47.0 mmol) were weighed, N-methyl-2-pyrrolidone (36 g) was added, and the temperature was maintained at 145°C under a nitrogen atmosphere. was reacted for 9 hours. After completion of the reaction, N-methyl-2-pyrrolidone (150 g) was added for dilution, and after removing salts by filtration, this solution was poured into methanol (3 kg). The precipitated solid was filtered, washed with a small amount of methanol, filtered again and collected, dried under the same conditions as in Synthesis Example 1, and polymer P having a structural unit represented by the following formula (P-2). -2 was obtained (yield 7.6 g, yield 48%, weight average molecular weight (Mw); 30,000, glass transition temperature (Tg); 232°C). The weight average molecular weight and glass transition temperature were measured in the same manner as in Synthesis Example 1.

<Synthesis Example 3>
1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane (BisTMC) (18.6 g, 60.0 mmol), 4,6- Dichloro-2-phenylpyrimidine (PhPym) (13.7 g, 61.1 mmol) and potassium carbonate (11.4 g, 82.5 mmol) were weighed, N-methyl-2-pyrrolidone (75 g) was added, and a nitrogen atmosphere was added. The mixture was reacted at 130° C. for 6 hours. After completion of the reaction, N-methyl-2-pyrrolidone (368 g) was added for dilution, and after removing salts by filtration, this solution was poured into methanol (9.1 kg). The precipitated solid was filtered off, washed with a small amount of methanol, filtered again and collected, dried under the same conditions as in Synthesis Example 1, and polymer P having a structural unit represented by the following formula (P-3): -3 was obtained (yield 20.5 g, yield 90%, weight average molecular weight (Mw); 187,000, glass transition temperature (Tg); 223°C). The weight average molecular weight and glass transition temperature were measured in the same manner as in Synthesis Example 1.

<Synthesis Example 4>
1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane (BisTMC) (12.4 g, 40.0 mmol), 2,2- bis(4-hydroxyphenyl)-propane (BisA) (2.3 g, 10.0 mmol), 1,1-bis(4-hydroxyphenyl)-decane (BisP-DED) (3.3 g, 10.0 mmol), 4,6-dichloro-2-phenylpyrimidine (PhPym) (13.7 g, 61.1 mmol) and potassium carbonate (11.4 g, 82.5 mmol) were weighed in and N-methyl-2-pyrrolidone (75 g) was added. In addition, they were reacted at 130° C. for 6 hours under a nitrogen atmosphere. After completion of the reaction, N-methyl-2-pyrrolidone (368 g) was added for dilution, and after removing salts by filtration, this solution was poured into methanol (9.1 kg). The precipitated solid was filtered, washed with a small amount of methanol, filtered again and collected, dried under the same conditions as in Synthesis Example 1, and the polymer P having a structural unit represented by the following formula (P-4): -4 was obtained (yield 23.5 g, yield 87%, weight average molecular weight (Mw); 165,000, glass transition temperature (Tg); 196°C). The weight average molecular weight and glass transition temperature were measured in the same manner as in Synthesis Example 1.

<Synthesis Example 5>
1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane (BisTMC) (12.4 g, 40.0 mmol), 4,4′ was added to a four-necked separable flask equipped with a stirrer. -(1,3-dimethylbutylidene)bisphenol (BisP-MIBK) (2.7 g, 10.0 mmol), 1,1-bis(4-hydroxyphenyl)-decane (BisP-DED) (3.3 g, 10 .0 mmol), 4,6-dichloro-2-phenylpyrimidine (PhPym) (13.7 g, 61.1 mmol), and potassium carbonate (11.4 g, 82.5 mmol) were weighed into N-methyl-2-pyrrolidone. (75 g) was added and reacted at 130° C. for 6 hours under nitrogen atmosphere. After completion of the reaction, N-methyl-2-pyrrolidone (368 g) was added for dilution, and after removing salts by filtration, this solution was poured into methanol (9.1 kg). The precipitated solid was filtered, washed with a small amount of methanol, filtered again and collected, dried under the same conditions as in Synthesis Example 1, and polymer P having a structural unit represented by the following formula (P-5). -5 was obtained (yield 23.8 g, yield 88%, weight average molecular weight (Mw); 157,000, glass transition temperature (Tg); 190°C). The weight average molecular weight and glass transition temperature were measured in the same manner as in Synthesis Example 1.

[Example 1]
945 parts of magnetic powder (manufactured by Epson Atmix Co., Ltd., product name "AW2-08PF8F", Fe--Cr--Si alloy (amorphous), average particle diameter: 5 μm, specific gravity: 7.0 g/cm ³ ) as core particles , Polymer P-1 50 parts, 2,2'-bis (4-cyanatophenyl) propane as a curable compound (manufactured by Tokyo Chemical Industry Co., Ltd.) 50 parts, 1-benzyl-2-methyl as a curing aid Five parts of imidazole (manufactured by Mitsubishi Chemical Corporation, product name “BMI 12”) and 160 parts of cyclopentanone (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed with a paint shaker to obtain a slurry liquid. After removing the solvent from the resulting slurry liquid by suction filtration using No5C filter paper manufactured by Advantech Toyo Co., Ltd., the collected particles were dried in a vacuum dryer at 40 ° C. for 12 hours to obtain an insulating film-covered magnetism. Got a filler.

[Example 2]
Polymer P-1 35 parts, SR-16H (manufactured by Sakamoto Yakuhin Kogyo Co., Ltd., epoxy equivalent: 160 g / eq) as a curable compound 65 parts, 1-benzyl-2-methylimidazole (BMI 12) as a curing aid 2.5 parts and 922.5 parts of methyl ethyl ketone (manufactured by Tokyo Kasei Kogyo Co., Ltd.) were mixed to obtain a spray solution.
1947.5 parts of magnetic powder (manufactured by Epson Atmix Co., Ltd., product name "AW2-08PF3F", Fe--Cr--Si alloy (amorphous), average particle size; 3 μm, specific gravity; 7.0 g/cm ³ ). , while stirring with a spiral stirring blade using a three-one motor, the resulting sprayed liquid is passed through a high-viscosity liquid atomization spray nozzle (amount of sprayed liquid: 1 mL / min, amount of air: 10 L / min). An insulating film-coated magnetic filler was obtained by air-drying at 60° C. while spraying using the powder.

[Example 3]
595 parts of magnetic powder (AW2-08PF8F) as core particles, 80 parts of polymer P-1, 20 parts of HP-4032D (manufactured by DIC Corporation, epoxy equivalent; 141 meq/g) as curing compound, 1 part as curing aid - 5 parts of benzyl-2-methylimidazole (BMI 12) and 420 parts of methyl ethyl ketone (manufactured by Tokyo Kasei Kogyo Co., Ltd.) are stirred at a pressure of 30 MPa and 40 ° C. for 2 hours while introducing CO ₂ using an autoclave. did. After stirring, CO ₂ was removed at 40° C., and after depressurization for drying, CO ₂ was flowed to dry the contents, followed by vacuum drying at 40° C. for 12 hours to obtain an insulating film. A coated magnetic filler was obtained.

[Examples 4 to 8]
An insulating film-coated magnetic filler was obtained in the same manner as in Example 1, except that the raw material of the slurry liquid was changed to the raw material shown in Table 1.

[Comparative Example 1]
1947.5 parts of magnetic powder (AW2-08PF3F) as core particles, 65 parts of novolac resin (manufactured by Gun Ei Chemical Industry Co., Ltd., product name "Resitop PSM-4261"), o-cresol novolak type epoxy as a curing compound Resin (manufactured by Nippon Steel Corporation, product name "YDCN-704") 34 parts, triphenylphosphine (manufactured by Tokyo Chemical Industry Co., Ltd.) 1 part as a curing aid, 80 with two rolls without adding a solvent The magnetic filler was obtained by kneading while heating to °C.

[Comparative Example 2]
Insulating film-coated magnetic filler was obtained in the same manner as in Example 1, except that the raw material of the slurry liquid was changed to the raw material shown in Table 1 and the slurry was not dried at 40° C. for 12 hours.

<B stage characteristics>
As the B-stage characteristics of the magnetic fillers obtained in Examples and Comparative Examples, the average particle size, calculated film thickness and calorific value were measured. Table 1 shows the results. The B-stage characteristic refers to a state in which the insulating film in the magnetic filler is semi-cured.

[Average particle size]
The average particle size shown in Table 1 is the average particle size of the magnetic powder used. The average particle size is the value measured by the method described above.

[Calculated film thickness]
The theoretical value of the film thickness of the coating layer in the magnetic fillers obtained in Examples and Comparative Examples was calculated from the average particle size of the magnetic powder used, the specific gravity of the magnetic powder used, and the specific gravity of the polymer used ( calculated film thickness). At this time, the specific gravity of the magnetic powder was calculated as 7.0 g/cm ³ and the specific gravity of the polymer as 1.2 g/cm ³ .

〔Calorific value〕
The magnetic fillers obtained in Examples and Comparative Examples were heated from 150° C. to 300° C. at a rate of 10° C./min using a DSC (differential scanning calorimeter), and the calorific value of the magnetic fillers was measured. was measured.
Magnetic fillers with a calorific value of 5 J/g or less result in poor adhesiveness between fillers after pressing when a molding is formed by pressing as shown in the following C-stage characteristics using the magnetic fillers. Therefore, magnetic fillers with a calorific value of 5 J/g or less were judged to be defective.

<C stage characteristics>
As the C-stage characteristics of the magnetic fillers obtained in Examples and Comparative Examples, dispersibility, relative magnetic permeability, loss factor, resistance value, embedded appearance and reliability were measured. Table 1 shows the results. Here, the C-stage characteristic refers to a state in which the insulating film in the magnetic filler is completely cured.

・Preparation of toroidal core Using a mold made of SKS3 alloy tool steel that has undergone mold release treatment, a toroidal core having an outer diameter of 18 mm, an inner diameter of 11 mm, and a height (thickness) of about 7 mm was obtained in the examples and comparative examples. The mold was filled with the magnetic filler obtained in . After filling, a toroidal core was produced by performing press treatment at 35 MPa for 90 minutes while heating the mold to 180° C. using a 26-ton hydraulic molding machine (manufactured by Toho Press Kogyo Co., Ltd.).

[Average shielding distance (dispersibility)]
SEM observation of the produced toroidal core was performed. For each SEM image obtained, the length of the resin layer existing between particles (shielding distance) is measured at 100 points, and the shielding distance in 100 SEM images measured in the same manner is arithmetically averaged. Thus, the average shielding distance was calculated.
When this average shielding distance is longer than the thickness of the insulating film forming the insulating-film-coated magnetic filler and is shorter than twice the thickness of the insulating film, it can be said that the magnetic particles have good dispersibility. It is easy to secure insulation as average shielding distance is more than the said minimum. Moreover, when the average shielding distance is equal to or less than the upper limit, it is easy to secure good magnetic permeability and loss factor. On the other hand, when the magnetic fillers were continuously connected to each other and not individually insulated, the measurement was not possible, so it was described as defective in the table.

[Relative permeability and loss factor]
Using the produced toroidal core, Keysight Technologies, Inc. Impedance analyzer "E4991B", and Keysight Technologies, Inc. magnetic material test fixture "16454A", measurement frequency from 1MHz to 1GHz The relative permeability (μ′) and magnetic permeability loss (μ″) were measured at a room temperature of 23° C., and the loss factor (tan δ) was calculated from the following formula.
tan δ=μ''/μ'
Table 1 shows the relative permeability and loss factor when the measurement frequency is 1 MHz, 20 MHz or 100 MHz. When the relative magnetic permeability is 2 or more, it can be judged to be good, and when the loss factor is 0.1 or less, it can be judged to be good.

[Resistance value and embedded appearance (evaluation of wiring board)]
On the wiring pattern side of a polyimide film (50 μm thick) on which a comb-shaped wiring pattern having a circuit (wiring pattern) having a line width of 25 μm, a space width of 25 μm, and a thickness of 12 μm is formed, The magnetic filler obtained in the comparative example was arranged so that the resulting insulating layer had a thickness of 50 μm, and after placing a PET film on it, a 26-ton hydraulic molding machine (manufactured by Toho Press Industry Co., Ltd. ) and pressurized at 35 MPa. After peeling off the PET film from the laminate formed by this pressurization, the magnetic filler layer was thermally cured by heat treatment at 185° C. for 60 minutes to obtain a wiring board having an insulating layer.
A voltage of 5 V was applied to the obtained wiring board, and resistance values were measured at seven points on the insulating layer of the wiring board. An average value of the resistance values obtained at seven points was calculated.
At this time, the wiring pattern was observed, and if voids and peeling were not observed in the wiring pattern, the embedded appearance was judged to be good.

[Reliability (TCT)]
Using a thermal cycle tester, a wiring board having an insulating layer prepared in the same manner as described above was cooled in a -40°C room for 30 minutes, moved from there to a 125°C room, and heated in a 125°C room for 30 minutes. Then, the step of moving to a room at −40° C. was defined as one cycle, and after repeating the cycle 500 times, the change in appearance of the insulating layer was confirmed by SEM images. Reliability was judged to be poor when foaming or cracks occurred in the insulating layer, and reliability was judged to be good when there was no change in the insulating layer around 500 cycles.
Also, changes in the average resistance value of the insulating layer at 7 locations around 500 cycles were confirmed. Reliability is good when the ratio of the average resistance value after 500 cycles to the average resistance value before 500 cycles (average resistance value after 500 cycles/average resistance value before 500 cycles) is less than 0.1. A ratio of 0.1 or more was judged to be unreliable.

[Example 9]
100 g of the insulating film-coated magnetic filler prepared in Example 4 and 10 g of acetone (manufactured by Tokyo Kasei Kogyo Co., Ltd.) were mixed for 30 minutes in a paint shaker to obtain a paste.

[Example 10]
100 g of the insulating film-coated magnetic filler prepared in Example 4, 2.4 g of SR-16H (manufactured by Sakamoto Yakuhin Kogyo Co., Ltd.), 0.1 g of 1-benzyl-2-methylimidazole (BMI 12), and acetone ( Tokyo Kasei Kogyo Co., Ltd.) was mixed with a paint shaker for 30 minutes to obtain a paste.

[Example 11]
100 g of the insulating film-coated magnetic filler prepared in Example 5 and 10 g of acetone (manufactured by Tokyo Kasei Kogyo Co., Ltd.) were mixed for 30 minutes in a paint shaker to obtain a paste.

[Example 12]
100 g of the insulating film-coated magnetic filler prepared in Example 5, 2.4 g of SR-16H (manufactured by Sakamoto Yakuhin Kogyo Co., Ltd.), 0.1 g of 1-benzyl-2-methylimidazole (BMI 12), and acetone ( Tokyo Kasei Kogyo Co., Ltd.) was mixed with a paint shaker for 30 minutes to obtain a paste.

[Comparative Example 3]
100 g of the magnetic filler prepared in Comparative Example 1 and 10 g of acetone (manufactured by Tokyo Kasei Kogyo Co., Ltd.) were mixed for 30 minutes in a paint shaker to obtain a paste.

[Comparative Example 4]
100 g of the magnetic filler prepared in Comparative Example 1, 1.2 g of o-cresol novolak type epoxy resin (YDCN-704), 0.2 g of triphenylphosphine (manufactured by Tokyo Chemical Industry Co., Ltd.), and acetone (Tokyo Chemical Industry Co., Ltd. Co., Ltd.) was mixed with a paint shaker for 30 minutes to obtain a paste.

<Production of wiring board>
On the wiring pattern side of a polyimide film (50 μm thick) on which a comb-shaped wiring pattern having a circuit (wiring pattern) having a line width of 25 μm, a space width of 25 μm, and a thickness of 12 μm is formed, The paste obtained in the comparative example was screen-printed so that the resulting insulating layer had a thickness of 50 μm, dried at 70° C. for 10 minutes, and then subjected to a 26-ton hydraulic molding machine (manufactured by Toho Press Industry Co., Ltd. ), a wiring board having an insulating layer was obtained by pressing for 90 minutes at 35 MPa while heating the mold to 180°C.
At this time, the wiring pattern was observed, and if voids and peeling were not observed in the wiring pattern, the embedding appearance was judged to be good.

<C stage characteristics>
Dispersibility, relative permeability, loss factor, resistance value and reliability were measured as C-stage characteristics of the pastes obtained in Examples and Comparative Examples. Table 2 shows the results. Here, the C-stage characteristic refers to a state in which the components constituting the paste are completely cured.

・Preparation of toroidal core Using a mold made of SKS3 alloy tool steel that has undergone mold release treatment, a toroidal core having an outer diameter of 18 mm, an inner diameter of 11 mm, and a height (thickness) of about 7 mm was obtained in the examples and comparative examples. The mold was filled with the paste obtained in . After filling, it is vacuum-dried at 60°C for 3 hours, and then pressed at 35 MPa for 90 minutes while heating the mold to 180°C using a 26-ton hydraulic molding machine (manufactured by Toho Press Industry Co., Ltd.). Thus, a toroidal core was produced.

Using the produced toroidal core, the average shielding distance (dispersibility), relative magnetic permeability and loss factor were measured in the same manner as in Example 1.

[Resistance value and embedded appearance (evaluation of wiring board)]
A voltage of 5 V was applied to a wiring board having an insulating layer prepared in the same manner as described above, and resistance values were measured at seven points on the insulating layer of the wiring board. An average value of the resistance values obtained at seven points was calculated.
At this time, the wiring pattern was observed, and if voids and peeling were not observed in the wiring pattern, the embedded appearance was judged to be good.

[Reliability (TCT)]
Using a thermal cycle tester, a wiring board having an insulating layer prepared in the same manner as described above was cooled in a -40°C room for 30 minutes, moved from there to a 125°C room, and heated in a 125°C room for 30 minutes. Then, the step of moving to a room at −40° C. was defined as one cycle, and after repeating the cycle 500 times, the change in appearance of the insulating layer was confirmed by SEM images. Reliability was judged to be poor when foaming or cracks occurred in the insulating layer, and reliability was judged to be good when there was no change in the insulating layer after about 500 cycles.
In addition, the ratio of the average resistance value after 500 cycles to the average resistance value before 500 cycles (average resistance value after 500 cycles/500 cycles The reliability was judged to be good when the previous average resistance value) was less than 0.1, and the reliability was judged to be poor when the ratio was 0.1 or more.

[Example 13]
100 g of the insulating film-coated magnetic filler prepared in Example 6 and 50 g of acetone (manufactured by Tokyo Kasei Kogyo Co., Ltd.) were stirred to prepare a magnetic filler dispersion.
This dispersion was applied onto a PET film using an applicator with a coating width of 12 cm with a gap of 150 μm, dried at 70° C. for 10 minutes and then at 120° C. for 10 minutes in an oven to form a magnetic film having a thickness of 100 μm. A sheet was produced.

[Example 14]
100 g of the insulating film-coated magnetic filler prepared in Example 6, 2.4 g of SR-16H (manufactured by Sakamoto Yakuhin Kogyo Co., Ltd.), 0.1 g of 1-benzyl-2-methylimidazole (BMI 12), and acetone ( Tokyo Kasei Kogyo Co., Ltd.) was stirred to prepare a magnetic filler dispersion.
A magnetic sheet was produced in the same manner as in Example 13, except that the obtained dispersion was used.

[Example 15]
100 g of the insulating film-coated magnetic filler prepared in Example 7 and 50 g of acetone (manufactured by Tokyo Kasei Kogyo Co., Ltd.) were stirred to prepare a magnetic filler dispersion.
A magnetic sheet was produced in the same manner as in Example 13, except that the obtained dispersion was used.

[Example 16]
100 g of the insulating film-coated magnetic filler prepared in Example 7, 2.4 g of SR-16H (manufactured by Sakamoto Yakuhin Kogyo Co., Ltd.), 0.1 g of 1-benzyl-2-methylimidazole (BMI 12), and acetone ( Tokyo Kasei Kogyo Co., Ltd.) was stirred to prepare a magnetic filler dispersion.
A magnetic sheet was produced in the same manner as in Example 13, except that the obtained dispersion was used.

[Comparative Example 5]
100 g of the magnetic filler prepared in Comparative Example 1 and 50 g of acetone (manufactured by Tokyo Kasei Kogyo Co., Ltd.) were stirred to prepare a magnetic filler dispersion.
A magnetic sheet was produced in the same manner as in Example 13, except that the obtained dispersion was used.

[Comparative Example 6]
100 g of the magnetic filler prepared in Comparative Example 1, 1.2 g of o-cresol novolak type epoxy resin (YDCN-704), 0.2 g of triphenylphosphine (manufactured by Tokyo Chemical Industry Co., Ltd.), and acetone (Tokyo Chemical Industry Co., Ltd. (manufactured by Co., Ltd.) was stirred to prepare a magnetic filler dispersion.
A magnetic sheet was produced in the same manner as in Example 13, except that the obtained dispersion was used.

<Production of wiring board>
On the wiring pattern side of a polyimide film (50 μm thick) on which a comb-shaped wiring pattern having a circuit (wiring pattern) having a line width of 25 μm, a space width of 25 μm, and a thickness of 12 μm is formed, After placing the magnetic sheet obtained in Comparative Example (with the PET film peeled off), pressurize at 180 ° C. and 35 MPa for 90 minutes using a 26-ton hydraulic molding machine (manufactured by Toho Press Industry Co., Ltd.). A wiring board having an insulating layer was obtained.
At this time, the wiring pattern was observed, and if voids and peeling were not observed in the wiring pattern, the embedding appearance was judged to be good.

<C stage characteristics>
Dispersibility, relative permeability, loss factor, resistance value and reliability were measured as C-stage characteristics of the magnetic sheets obtained in Examples and Comparative Examples. Table 3 shows the results. Here, the C-stage characteristic refers to the state in which the magnetic sheet is completely cured.

・Preparation of toroidal core Using a mold made of SKS3 alloy tool steel that has undergone mold release treatment, a toroidal core having an outer diameter of 18 mm, an inner diameter of 11 mm, and a height (thickness) of about 7 mm was obtained in the examples and comparative examples. The magnetic sheet (from which the PET film was peeled) obtained in 1. was filled in a mold. After filling, a toroidal core was produced by performing press treatment at 35 MPa for 90 minutes while heating the mold to 180° C. using a 26-ton hydraulic molding machine (manufactured by Toho Press Kogyo Co., Ltd.).

Using the produced toroidal core, the average shielding distance (dispersibility), relative magnetic permeability and loss factor were measured in the same manner as in Example 1.

[Resistance value and embedded appearance (evaluation of wiring board)]
A voltage of 5 V was applied to a wiring board having an insulating layer prepared in the same manner as described above, and resistance values were measured at seven points on the insulating layer of the wiring board. An average value of the resistance values obtained at seven points was calculated.
At this time, the wiring pattern was observed, and if voids and peeling were not observed in the wiring pattern, the embedded appearance was judged to be good.

[Reliability (TCT)]
Using a thermal cycle tester, a wiring board having an insulating layer prepared in the same manner as described above is cooled in a -40 ° C. room for 30 minutes, moved from there to a 125 ° C. room, and heated in a 125 ° C. room for 30 minutes. Then, the step of moving to a room at −40° C. was defined as one cycle, and after repeating the cycle 500 times, the change in appearance of the insulating layer was confirmed by SEM images. Reliability was judged to be poor when foaming or cracks occurred in the insulating layer, and reliability was judged to be good when there was no change in the insulating layer after about 500 cycles.
Also, changes in the average resistance value of the insulating layer at 7 locations around 500 cycles were confirmed. Reliability is good when the ratio of the average resistance value after 500 cycles to the average resistance value before 500 cycles (average resistance value after 500 cycles/average resistance value before 500 cycles) is less than 0.1. A ratio of 0.1 or more was judged to be unreliable.

Abbreviations in Tables 1 to 3 are as follows.

<Polymer>
-Polymer A: Maleic acid-modified styrene-ethylene butylene-styrene block copolymer (manufactured by Asahi Kasei Corporation, product name "Tuftec M1913")
・Polymer B: novolak resin (manufactured by Gun Ei Chemical Industry Co., Ltd., product name “Regitop PSM-4261”)

<Curable compound>
- Compound A: 2,2'-bis (4-cyanatophenyl) propane (manufactured by Tokyo Chemical Industry Co., Ltd.)
- Compound B: SR-16H (manufactured by Sakamoto Pharmaceutical Co., Ltd., epoxy equivalent: 160 g / eq)
-Compound C: HP-4032D (manufactured by DIC Corporation, epoxy equivalent: 141 meq / g)
- Compound D: SR-4PG (manufactured by Sakamoto Yakuhin Kogyo Co., Ltd., epoxy equivalent: 305 g / eq)
・Compound E: o-cresol novolac type epoxy resin (manufactured by Nippon Steel Corporation, product name “YDCN-704”)

<Curing aid>
- Curing aid A: 1-benzyl-2-methylimidazole (manufactured by Mitsubishi Chemical Corporation, product name "BMI 12")
・ Curing aid B: Zinc 2-ethyloctylate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)
・ Curing aid C: triphenylphosphine (manufactured by Tokyo Chemical Industry Co., Ltd.)

<Solvent>
- Solvent A: cyclopentanone (manufactured by Tokyo Chemical Industry Co., Ltd.)
・ Solvent B: methyl ethyl ketone (manufactured by Tokyo Chemical Industry Co., Ltd.)
・ Solvent C: acetone (manufactured by Tokyo Chemical Industry Co., Ltd.)

<Magnetic powder>
・Magnetic powder A: AW2-08PF8F (manufactured by Epson Atmix Corporation, Fe--Cr--Si alloy (amorphous), average particle size: 5 μm, specific gravity: 7.0 g/cm ³ )
・Magnetic powder B: AW2-08PF3F (manufactured by Epson Atmix Corporation, Fe--Cr--Si alloy (amorphous), average particle size: 3 μm, specific gravity: 7.0 g/cm ³ )
・Magnetic powder C: AW2-08PF20F (manufactured by Epson Atmix Corporation, Fe--Cr--Si alloy (amorphous), average particle size: 11 μm, specific gravity: 7.0 g/cm ³ )

From the results of Tables 1 to 3, according to the present materials obtained in Examples 1 to 16, not only can high magnetic permeability and low loss coefficient be achieved, but also the embedding property is good and the reliability is high. It was confirmed that an inductor wiring board having excellent adhesion to the substrate could be produced. On the other hand, in the case of using the magnetic material containing no polymer (B) of Comparative Examples 1 to 4, it was confirmed that the embedding appearance was poor and the reliability was inferior.

The present invention is not limited to the above embodiments, and various modifications are possible. The present invention includes configurations substantially the same as the configurations described in the embodiments (for example, configurations with the same function, method and result, or configurations with the same purpose and effect). The present invention also includes configurations in which non-essential portions of the configurations described in the above embodiments are replaced with other configurations. Furthermore, the present invention also includes a configuration that achieves the same effects or achieves the same purpose as the configurations described in the above embodiments. Furthermore, the present invention also includes configurations obtained by adding known techniques to the configurations described in the above embodiments.

Claims (10)

Magnetic powder (A) and polymer (B) having at least one type of repeating unit among repeating units represented by the following formulas (1-1), (1-2) and (1-3) magnetic material.

[In formulas (1-1) to (1-3), R ¹ is each independently a halogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, or a monovalent halogenated group having 1 to 20 carbon atoms. Hydrocarbon groups, groups partially substituted with at least one selected from oxygen atoms and sulfur atoms in these hydrocarbon groups or halogenated hydrocarbon groups, nitro groups, cyano groups, amino groups, or salts of amino groups is. Each n is independently an integer of 0-2. When n is 2, multiple R ¹ may be the same or different, and may be combined in any combination to form a part of the ring structure. A ¹ and A ² are each independently -O-, -S- or -N(R ² )- [R ² is a hydrogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, a carbon It is a monovalent halogenated hydrocarbon group of number 1 to 20, or a group partially substituted with at least one selected from oxygen and sulfur atoms in these hydrocarbon groups or halogenated hydrocarbon groups. ]. X is a divalent organic group. ] The magnetic material is
A magnetic composition containing the magnetic powder (A) and the polymer (B), or
A magnetic filler comprising the magnetic powder (A) and a coating layer containing the polymer (B) covering the magnetic powder (A).
A magnetic material according to claim 1 . 3. The magnetic material according to claim 1, wherein X in formulas (1-1) to (1-3) contains a group represented by formula (2-1) below.

[In formula (2-1), Ar ₁ and Ar ₂ are each independently a substituted or unsubstituted aromatic hydrocarbon group. L is a single bond, -O-, -S-, -N(R ⁸ )-, -C(O)-, -C(O)-O-, -C(O)-NH-, -S( O)-, -S(O) ₂ -, -P(O)-, or a divalent organic group [R ⁸ is a hydrogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, or , is a monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms. ]. y is an integer from 0 to 5; When y is 2 or more, a plurality of L's may be the same or different. R ⁶ and R ⁷ are each independently a single bond, a methylene group, or an alkylene group having 2 to 4 carbon atoms. ] The magnetic material according to any one of claims 1 to 3, wherein the magnetic powder (A) contains an iron element. 3. The magnetic material according to claim 2, wherein said magnetic composition or said coating layer further contains a curable compound (C) and a curing aid (D). The curable compound (C) is at least one selected from the group consisting of epoxy compounds, cyanate ester compounds, vinyl compounds, silicone compounds, oxazine compounds, maleimide compounds, allyl compounds, oxetane compounds, methylol compounds and propargyl compounds. A magnetic material according to claim 5. 3. The magnetic material according to claim 2, wherein said magnetic composition further contains a solvent (E). A magnetic member formed from the magnetic material according to any one of claims 1 to 7. A coil comprising the magnetic member according to claim 8 . An inductor wiring board comprising the magnetic member according to claim 8 or the coil according to claim 9.