Composition, magnetic particle-containing cured product, and electronic component

A magnetic particle composition with high iron content and tailored particle size distribution, combined with an epoxy resin, addresses low permeability and high loss issues, providing improved magnetic properties and embeddability for electronic components.

JP7828299B2Active Publication Date: 2026-03-11FUJIFILM CORP
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Patent Information

Authority / Receiving Office
JP · JP
Patent Type
Patents
Current Assignee / Owner
Filing Date
2021-12-22
Publication Date
2026-03-11

AI Technical Summary

Technical Problem

Existing magnetic particle-containing compositions exhibit low magnetic permeability and high magnetic loss, and lack excellent embeddability for applications in circuit board holes.

Method used

A composition comprising magnetic particles with a high iron content (70% by mass or more) and specific particle size distribution, combined with an epoxy resin, which can form a cured product with high magnetic permeability and low magnetic loss, and excellent embeddability.

Benefits of technology

The composition forms a cured product with enhanced magnetic permeability, reduced magnetic loss, and improved embeddability, suitable for applications in electronic components.

✦ Generated by Eureka AI based on patent content.

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Abstract

The present invention addresses the problem of providing a composition with which a magnetic-particle-containing cured product that has high magnetic permeability and low magnetic loss can be formed and which has excellent suitability for embedding. The present invention also addresses the problem of providing a magnetic-particle-containing cured product and an electronic component. A composition according to the present invention contains an epoxy resin and magnetic particles containing at least 70 mass% of Fe atoms, wherein the magnetic particles have a peak top in the range of 10-30 μm in a particle size distribution curve representing a volume-based frequency distribution, and the magnetic particle content is 70-90 mass% relative to the total solid content in the composition.
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Description

[Technical Field]

[0001] The present invention relates to a composition, a magnetic particle-containing cured product, and an electronic component. [Background technology]

[0002] As electronic devices become more compact and powerful, the integration density of electronic circuits is increasing. Coating-type compositions containing magnetic particles are one of the materials that can improve integration density. The use of such compositions allows magnetic materials to be mounted in any shape, making it easier to achieve smaller, more powerful electronic devices than the conventional method of placing individual magnetic particles on a chip.

[0003] Examples of coating compositions containing magnetic particles include compositions for filling through holes in circuit boards for inductor components and the like. For example, Patent Document 1 discloses a composition for filling through holes, which is a magnetic paste containing "(A) magnetic powder having an average particle size of 1 μm or more, (B) epoxy resin, (C) reactive diluent, (D) curing agent, and (E) filler having an average particle size of less than 1 μm." [Prior art documents] [Patent documents]

[0004] [Patent Document 1] International Publication No. 2020 / 105704 Summary of the Invention [Problem to be solved by the invention]

[0005] Recently, the present inventors have prepared and examined compositions with reference to Patent Document 1, and have found that the magnetic permeability of magnetic particle-containing cured products formed from the compositions may be low. In other words, they have found that there is room for further improvement in the magnetic permeability of magnetic particle-containing cured products formed from the above compositions.

[0006] Incidentally, magnetic particle-containing cured materials formed from compositions containing magnetic particles are also required to have low magnetic loss. Furthermore, in view of applications as compositions for filling holes such as via holes and through holes in circuit boards for inductor components, compositions containing magnetic particles are required to have excellent embedding suitability.

[0007] Therefore, an object of the present invention is to provide a composition that can form a cured product containing magnetic particles with high magnetic permeability and low magnetic loss, and that also has excellent embeddability. Another object of the present invention is to provide a magnetic particle-containing cured product and an electronic component. [Means for solving the problem]

[0008] As a result of extensive research into solving the above problems, the present inventors have found that the above problems can be solved by the following configuration.

[0009] [1] A composition comprising magnetic particles containing 70% by mass or more of Fe atoms and an epoxy resin, the magnetic particles have a peak top in the range of 10 to 30 μm in a particle size distribution curve representing a volume-based frequency distribution, A composition in which the content of the magnetic particles is 70 to 90 mass % based on the total solid content of the composition. [2] The composition according to [1], wherein the magnetic particles contain 70 to 95 mass % Fe atoms. [3] The magnetic particles have a plurality of peak tops in a particle size distribution curve representing a volume-based frequency distribution, [1] The composition according to [2], wherein, among the plurality of peak tops, the particle diameter at the peak top Pmin having the smallest particle diameter is defined as Dmin, and the particle diameter at the peak top Pmax having the largest particle diameter is defined as Dmax / Dmin is 2 or more. [4] The composition according to [3], wherein the Dmax is in the range of 10 to 30 μm and the Dmin is in the range of 1 to 9 μm. [5] The composition according to any one of [1] to [4], further comprising a reactive diluent. [6] The composition according to any one of [1] to [5], further comprising a curing agent. [7] A magnetic particle-containing cured product formed using the composition according to any one of [1] to [6]. [8] An electronic component comprising the magnetic particle-containing cured material according to [7]. [9] The electronic component according to [8], which is used as an inductor.

[10] The electronic component according to [8], which is used as an antenna. [Effects of the Invention]

[0010] According to the present invention, it is possible to provide a composition that can form a cured product containing magnetic particles with high magnetic permeability and low magnetic loss, and that also has excellent embeddability. Furthermore, the present invention can provide a magnetic particle-containing cured product and an electronic component. [Brief explanation of the drawings]

[0011] [Figure 1] FIG. 2 is a particle size distribution diagram showing an example of a frequency distribution curve of specific magnetic particles contained in the composition of the present invention. [Figure 2] FIG. 2 is a particle size distribution diagram showing an example of a frequency distribution curve of specific magnetic particles contained in the composition of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0012] The present invention will be described in detail below. The following description of the components may be based on a representative embodiment of the present invention, but the present invention is not limited to such an embodiment. In the present specification, when a group (atomic group) is described without specifying whether it is substituted or unsubstituted, it encompasses both unsubstituted and substituted groups, unless it is contrary to the spirit of the present invention. For example, the term "alkyl group" encompasses not only unsubstituted alkyl groups (unsubstituted alkyl groups) but also substituted alkyl groups (substituted alkyl groups). Furthermore, the term "organic group" in the present specification refers to a group containing at least one carbon atom.

[0013] As used herein, "actinic rays" or "radiation" refers to, for example, the bright line spectrum of a mercury lamp, far ultraviolet light typified by excimer lasers, extreme ultraviolet light (EUV light: Extreme Ultraviolet), X-rays, and electron beams (EB). As used herein, "light" refers to actinic rays or radiation. Unless otherwise specified, the term "exposure" in this specification includes not only exposure to the bright line spectrum of a mercury lamp, far ultraviolet light represented by an excimer laser, extreme ultraviolet light, X-rays, EUV light, and the like, but also drawing with particle beams such as electron beams and ion beams.

[0014] In this specification, the symbol "to" is used to mean that the numerical values ​​before and after it are included as the lower limit and upper limit.

[0015] In this specification, the "solid content" of a composition refers to the components that form a cured product. Therefore, when a composition contains a solvent (organic solvent, water, etc.), it refers to all components excluding the solvent. Note that liquid components are also considered to be solids as long as they form a cured product.

[0016] In this specification, "boiling point" means the normal boiling point unless otherwise specified.

[0017] In this specification, the weight average molecular weight (Mw) is a value calculated as polystyrene by GPC (Gel Permeation Chromatography).

[0018] In addition, in this specification, unless otherwise specified, each component may be used alone or in combination of two or more substances corresponding to the component. Here, when two or more substances are used in combination for each component, the content of that component refers to the total content of the substances used in combination, unless otherwise specified.

[0019] [Composition] The composition of the present invention comprises: A composition comprising magnetic particles containing 70% by mass or more of Fe atoms (hereinafter also referred to as "specific magnetic particles") and an epoxy resin, The specific magnetic particles have a peak top in the range of 10 to 30 μm in a particle size distribution curve that represents a volume-based frequency distribution, The content of the specific magnetic particles is 70 to 90 mass % based on the total solid content in the composition.

[0020] The inventors have now demonstrated, through extensive research, that the composition described above can form a magnetic particle-containing cured product with high magnetic permeability and low magnetic loss, and also has excellent embeddability. When the specific magnetic particles have a peak in the range of 10 to 30 μm in a particle size distribution curve representing a volume-based frequency distribution, the magnetic particle-containing cured product formed from the composition has high magnetic permeability and low magnetic loss. Furthermore, when the content of the specific magnetic particles is 70 mass% or more relative to the total solid content of the composition, the magnetic particle-containing cured product formed from the composition has high magnetic permeability. On the other hand, when the content of the specific magnetic particles is 90 mass% or less relative to the total solid content of the composition, the composition has excellent embeddability. Hereinafter, a higher magnetic permeability of the magnetic particle-containing cured product formed from the composition, a lower magnetic loss of the magnetic particle-containing cured product formed from the composition, and / or a better embeddability of the composition is also referred to as "the effect of the present invention being better."

[0021] First, the various components contained in the composition will be described below.

[0022] [Specified magnetic particles] The composition contains magnetic particles (specific magnetic particles) containing 70 mass % or more of Fe atoms (hereinafter also referred to as "iron atoms"). The iron atoms may be contained in the magnetic particles as an alloy containing iron atoms (preferably a magnetic alloy containing iron atoms), an iron oxide (preferably a magnetic iron oxide), an iron nitride (preferably a magnetic iron nitride), or an iron carbide (preferably a magnetic iron carbide). The iron atom content is 70 mass% or more relative to the total mass of the specific magnetic particles. When the iron atom content is 70 mass% or more relative to the total mass of the specific magnetic particles, the magnetic particle-containing cured product formed from the composition has excellent magnetic permeability. The lower limit of the iron atom content is preferably 75% by mass or more, and more preferably 80% by mass or more, relative to the total mass of the specific magnetic particles.The upper limit of the iron atom content is preferably 95% by mass or less, more preferably 92% by mass or less, even more preferably 90% by mass or less, and particularly preferably 88% by mass or less, relative to the total mass of the specific magnetic particles, in order to improve the acid resistance of the magnetic particle-containing cured product formed from the composition.

[0023] The specific magnetic particles may contain metal atoms other than iron atoms. The term "other metal atoms" as used herein also includes metalloid atoms such as boron, silicon, germanium, arsenic, antimony, and tellurium. The other metal atoms may be contained in the magnetic particles as an alloy (preferably a magnetic alloy), a metal oxide (preferably a magnetic oxide), a metal nitride (preferably a magnetic nitride), or a metal carbide (preferably a magnetic carbide) containing the metal atoms.

[0024] The lower limit of the metal atom content (total content of iron atoms and other metal atoms) in the specific magnetic particles is 70% by mass or more, preferably 75% by mass or more, and more preferably 80% by mass or more, based on the total mass of the specific magnetic particles. The upper limit of the metal atom content (iron atoms and other metal atoms) is preferably 100% by mass or less, and more preferably 95% by mass or less, based on the total mass of the specific magnetic particles.

[0025] In addition, examples of materials other than iron atoms that make up the specific magnetic particles include Ni, Co, Al, Si, S, Sc, Ti, V, Cu, Y, Mo, Rh, Pd, Ag, Sn, Sb, Te, Ba, Ta, W, Re, Au, Bi, La, Ce, Pr, Nd, P, Zn, Sr, Zr, Mn, Cr, Nb, Pb, Ca, B, C, N, and O. The specific magnetic particles preferably contain one or more atoms selected from the group consisting of Si, Cr, C, P, Cu, Nb, and B as materials other than iron atoms.

[0026] The content of each metal atom in a specific magnetic particle can be identified by high-frequency inductively coupled plasma (ICP) emission spectroscopy.

[0027] Specific examples of materials constituting the specific magnetic particles include Fe-Co alloys, Fe-Ni alloys, Fe-Zr alloys, Fe-Mn alloys, Fe-Si alloys, Fe-Al alloys, Ni-Mo alloys, Fe-Ni-Co alloys, Fe-Si-Cr alloys, Fe-Si-B alloys, Fe-Si-Al alloys, Fe-Si-BC alloys, Fe-Si-B-Cr alloys, Fe-Si-B-Cr-C alloys, Fe-Co-Si-B alloys, Fe-Si-B-Nb alloys, Fe nanocrystalline alloys, Fe-based amorphous alloys, and ferrites such as spinel ferrites (preferably Ni-Zn ferrites and Mn-Zn ferrites) and hexagonal ferrites (preferably barium ferrites).The above alloys may be amorphous. Among these, alloys are preferred in that the magnetic particle-containing cured material formed from the composition has better magnetic permeability, with Fe-based amorphous alloys, Fe-Si-Cr alloys, Fe nanocrystalline alloys, and Fe-Ni-Co alloys being more preferred, and Fe-based amorphous alloys, Fe-Si-Cr alloys, and Fe nanocrystalline alloys being even more preferred.

[0028] The specific magnetic particles may have a surface layer formed on their surfaces. By having the specific magnetic particles have a surface layer in this way, the specific magnetic particles can be endowed with a function according to the material of the surface layer. The surface layer may be an inorganic layer or an organic layer.

[0029] As the inorganic layer-forming compound, metal oxides, metal nitrides, metal carbides, metal phosphate compounds, metal borate compounds, or silicate compounds (e.g., silicate esters such as tetraethyl orthosilicate, and silicates such as sodium silicate) are preferred because they can form a surface layer that is excellent in at least one of insulation, gas barrier properties, and chemical stability. Specific examples of elements contained in these compounds include Fe, Al, Ca, Mn, Zn, Mg, V, Cr, Y, Ba, Sr, Ge, Zr, Ti, Si, and rare earth elements. Materials constituting the inorganic layer obtained using the inorganic layer-forming compound include silicon oxide, germanium oxide, titanium oxide, aluminum oxide, zirconium oxide, and magnesium oxide, and the inorganic layer may be a layer containing two or more of these.

[0030] Examples of the organic layer-forming compound include acrylic monomers. Specific examples of the acrylic monomer include the compounds described in paragraphs 0022 and 0023 of JP-A-2019-067960. Examples of materials constituting the organic layer obtained using the organic layer-forming compound include acrylic resins.

[0031] The thickness of the surface layer is not particularly limited, but is preferably 3 to 1000 nm in order to allow the surface layer to exhibit its functions more effectively.

[0032] <Particle size distribution> The specific magnetic particles have a peak top in the range of 10 to 30 μm in a particle size distribution curve that represents a volume-based frequency distribution. In this specification, the particle size distribution curve that represents a volume-based frequency distribution is also referred to as a "frequency distribution curve." 1 and 2 are particle size distribution diagrams showing examples of frequency distribution curves of specific magnetic particles contained in the composition of the present invention. As shown in Fig. 1 and Fig. 2, the frequency distribution curve is expressed as a particle size distribution diagram with the particle diameter on the horizontal axis and the frequency (%) on the vertical axis. The frequency distribution curve can be obtained by measuring the composition of the present invention using a laser diffraction / scattering particle size distribution analyzer (product name "LA960N", manufactured by Horiba, Ltd.) in a measurement range mode of 0.01 μm to 5000 μm. For the measurement, if necessary, the composition may be diluted with PGMEA (propylene glycol monomethyl ether acetate) and subjected to ultrasonic dispersion for 60 minutes to prepare a dispersion, which may then be used as the measurement sample.

[0033] The peak top in a frequency distribution curve means the maximum point in the frequency distribution curve. In the example of Fig. 1, the frequency distribution curve has one peak top, but the number of peak tops is not limited to this. As shown in Fig. 1, when the frequency distribution curve has one peak top, the peak top (corresponding to P in Fig. 1) appears in the particle diameter range of 10 to 30 µm. When the frequency distribution curve has one peak top, the particle diameter at the peak top is preferably in the range of 10 to 20 μm, in order to further reduce the magnetic loss of the magnetic particle-containing cured material formed from the composition. When the frequency distribution curve has one peak top, the peak top is preferably in the particle diameter range of 12 to 30 μm, as this will result in a higher magnetic permeability of the magnetic particle-containing cured product formed from the composition. When the frequency distribution curve has one peak top, the particle diameter at the peak top is preferably in the range of 12 to 20 μm, since the magnetic particle-containing cured material formed from the composition has higher magnetic permeability and lower magnetic loss.

[0034] Furthermore, there may be multiple peak tops in the frequency distribution curve. In the example of Figure 2, the frequency distribution curve has two peak tops: the peak top Pmin with the smallest particle diameter and the peak top Pmax with the largest particle diameter. When the frequency distribution curve has multiple peak tops, where Dmin is the particle diameter at the smallest peak top Pmin and Dmax is the particle diameter at the largest peak top Pmax, the ratio of Dmax to Dmin (Dmax / Dmin) is preferably 2 or more, in order to enhance the effects of the present invention. When the ratio (Dmax / Dmin) is 2 or more, the gaps formed by the specific magnetic particles with relatively large particle diameters are filled by the specific magnetic particles with relatively small particle diameters, thereby further reducing the magnetic loss of the magnetic particle-containing cured product formed from the composition. The ratio (Dmax / Dmin) is more preferably 3 or more, and even more preferably 4 or more, in order to enhance the effects of the present invention. The upper limit of the ratio (Dmax / Dmin) is preferably 50 or less, more preferably 30 or less, even more preferably 20 or less, and particularly preferably 10 or less, in terms of achieving better effects of the present invention. In order to obtain a more excellent effect of the present invention, Dmax is preferably in the range of 10 to 30 μm, and Dmin is preferably in the range of 1 to 9 μm, and more preferably Dmin is in the range of 1 to 5 μm. The ratio (Dmax / Dmin) can be adjusted to fall within the above range, for example, by using a plurality of specific magnetic particles with different primary particle sizes and adjusting the blending ratio thereof as appropriate.

[0035] The specific magnetic particles may be used alone or in combination of two or more types.

[0036] The composition preferably contains at least specific magnetic particles having a volume-based median diameter (D50) of 10 to 30 μm (hereinafter also referred to as "specific magnetic particles A"). Here, the volume-based median diameter (D50) of specific magnetic particles A refers to the diameter at which the total volume of specific magnetic particles A on the larger diameter side and the smaller diameter side is equal when the entire specific magnetic particles A are divided into two parts using a threshold particle diameter at which the cumulative volume is 50%. The volume-based median diameter (D50) of specific magnetic particles A can be measured using a laser diffraction / scattering particle size distribution analyzer (for example, the laser diffraction / scattering particle size distribution analyzer LA-960 (model number) manufactured by Horiba, Ltd.). The average particle size (D50) of the specific magnetic particles A is preferably 12 to 20 μm, in order to obtain a better effect of the present invention. When the composition contains specific magnetic particles A as the specific magnetic particles, it is easy to obtain a frequency distribution curve with a peak top in the particle diameter range of 10 to 30 μm.

[0037] The composition also preferably contains, as specific magnetic particles, at least specific magnetic particles (hereinafter also referred to as "specific magnetic particles B") having a volume-based median diameter (D50) of 1 to 9 μm in addition to the above-mentioned specific magnetic particles A. The definition and measurement method of the volume-based median diameter (D50) of specific magnetic particles B are the same as those of the above-mentioned specific magnetic particles A. The average particle size (D50) of the specific magnetic particles B is preferably 1 to 5 μm, in order to obtain a better effect of the present invention. When the composition contains specific magnetic particles A and specific magnetic particles B as the specific magnetic particles, it is easy to obtain a frequency distribution curve in which Dmax is in the range of 10 to 30 μm and Dmin is in the range of 1 to 9 μm, as described above.

[0038] The content of the specific magnetic particles in the composition (the total content when multiple types of specific magnetic particles are included) is 70 to 90% by mass relative to the total solid content in the composition. In particular, the lower limit of the content of the specific magnetic particles is preferably 75% by mass or more, and more preferably 80% by mass or more, in order to improve the magnetic permeability of the magnetic particle-containing cured product formed from the composition. Furthermore, the upper limit of the content of the specific magnetic particles is more preferably 88% by mass or less, in order to improve the embeddability of the composition. The content of the specific magnetic particles in the composition is preferably 70 to 90% by mass relative to the total mass of the composition.

[0039] When the specific magnetic particles include specific magnetic particles A, the lower limit of the content of specific magnetic particles A is preferably 30% by mass or more, more preferably 40% by mass or more, even more preferably 60% by mass or more, and particularly preferably 80% by mass or more, relative to the total mass of the specific magnetic particles. The upper limit is not particularly limited, but is, for example, 100% by mass or less. When the specific magnetic particles include specific magnetic particles B, the upper limit of the content of specific magnetic particles B is preferably 70% by mass or less, more preferably 60% by mass or less, even more preferably 55% by mass or less, and particularly preferably 50% by mass or less, relative to the total mass of the specific magnetic particles. The lower limit is not particularly limited, but is, for example, 1% by mass or less, preferably 5% by mass or more, more preferably 15% by mass or more, and even more preferably 20% by mass or more. By including specific magnetic particles A and specific magnetic particles B in the composition and appropriately adjusting the compounding ratio of specific magnetic particles A to specific magnetic particles B, it is easy to obtain a frequency distribution curve in which the ratio (Dmax / Dmin) is 2 or more, as described above.

[0040] [Epoxy resin] The composition includes an epoxy resin. Examples of epoxy resins include bisphenol A type epoxy resins; bisphenol F type epoxy resins; bisphenol S type epoxy resins; bisphenol AF type epoxy resins; dicyclopentadiene type epoxy resins; trisphenol type epoxy resins; phenol novolac type epoxy resins; tert-butyl-catechol type epoxy resins; epoxy resins having a condensed ring structure such as naphthol novolac type epoxy resins, naphthalene type epoxy resins, naphthol type epoxy resins, and anthracene type epoxy resins; glycidyl amine type epoxy resins; glycidyl ester type epoxy resins; cresol novolac type epoxy resins; biphenyl type epoxy resins; linear aliphatic epoxy resins; epoxy resins having a butadiene structure; alicyclic epoxy resins; heterocyclic epoxy resins; spiro ring-containing epoxy resins; cyclohexanedimethanol type epoxy resins; trimethylol type epoxy resins; and tetraphenylethane type epoxy resins. The epoxy resin is preferably at least one selected from bisphenol A type epoxy resins and bisphenol F type epoxy resins.

[0041] The epoxy resin preferably contains an epoxy resin having two or more epoxy groups in one molecule. Furthermore, the epoxy resin preferably has an aromatic structure, and when two or more epoxy resins are used, it is more preferable that at least one of them has an aromatic structure. An aromatic structure is a chemical structure generally defined as aromatic, and also includes polycyclic aromatic rings and aromatic heterocycles.

[0042] Epoxy resins include epoxy resins that are liquid at a temperature of 25°C (hereinafter also referred to as "liquid epoxy resins") and epoxy resins that are solid at a temperature of 25°C (hereinafter also referred to as "solid epoxy resins"). The composition may contain either a liquid epoxy resin or a solid epoxy resin as the epoxy resin, but it is preferable that the composition contain only a liquid epoxy resin, as this will provide better effects of the present invention. As the liquid epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, phenol novolac type epoxy resin, alicyclic epoxy resin having an ester skeleton, cyclohexanedimethanol type epoxy resin, or epoxy resin having a butadiene structure is preferred, and glycidyl amine type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, or bisphenol AF type epoxy resin is more preferred.

[0043] Specific examples of liquid epoxy resins include "HP4032," "HP4032D," and "HP4032SS" (naphthalene-type epoxy resins) manufactured by DIC Corporation; "828US" and "jER828EL" (bisphenol A-type epoxy resins), "jER807" (bisphenol F-type epoxy resins), and "jER152" (phenol novolac-type epoxy resins) manufactured by Mitsubishi Chemical Corporation; "630" and "630LSD" (glycidylamine-type epoxy resins) manufactured by Mitsubishi Chemical Corporation; "ZX-1059" (a mixture of bisphenol A-type epoxy resin and bisphenol F-type epoxy resin) manufactured by Nippon Steel Chemical & Material Co., Ltd.; "EX-721" (glycidyl ester-type epoxy resin) manufactured by Nagase ChemteX Corporation; and "PB-3600" (epoxy resin having a butadiene structure) and "EHPE 3150" (alicyclic epoxy resin) manufactured by Daicel Corporation.

[0044] Examples of solid epoxy resins include naphthalene-type tetrafunctional epoxy resins, cresol novolac-type epoxy resins, dicyclopentadiene-type epoxy resins, trisphenol-type epoxy resins, naphthol-type epoxy resins, biphenyl-type epoxy resins, naphthylene ether-type epoxy resins, anthracene-type epoxy resins, bisphenol A-type epoxy resins, and tetraphenylethane-type epoxy resins. Specific examples of solid epoxy resins include "HP4032H" (naphthalene type epoxy resin), "HP-4700" and "HP-4710" (naphthalene type tetrafunctional epoxy resin), "N-690" and "N-695" (cresol novolac type epoxy resin), "HP-7200", "HP-7200HH", and "HP-7200H" (dicyclopentadiene type epoxy resin), as well as "EXA-7311", "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S", and "HP6000" (naphthylene ether type epoxy resin), all manufactured by DIC Corporation; and "EPPN-502H" (trisphenol type epoxy resin), "NC7000L" (naphthol novolac type epoxy resin), as well as "NC3000H", "NC3000", "NC3000L", and " Examples include "NC3100" (biphenyl-type epoxy resin); "ESN475V" (naphthalene-type epoxy resin) and "ESN485" (naphthol novolac-type epoxy resin) manufactured by Nippon Steel Chemical & Material Co., Ltd.; "YX4000H" and "YL6121" (biphenyl-type epoxy resin), "YX4000HK" (bixylenol-type epoxy resin), and "YX8800" (anthracene-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "PG-100" and "CG-500" (bisphenol AF-type epoxy resin) manufactured by Osaka Gas Chemicals Co., Ltd.; "YL7760" (bisphenol AF-type epoxy resin), "YL7800" (fluorene-type epoxy resin), "jER1010" (solid bisphenol A-type epoxy resin), and "jER1031S" (tetraphenylethane-type epoxy resin) manufactured by Mitsubishi Chemical Corporation.

[0045] In addition to the epoxy resins described above, the epoxy resins that can be used include the Epochalic series "THI-DE", "DE-102", and "DE-103" (alicyclic epoxy compounds) manufactured by ENEOS Corporation, as well as the epoxy compounds described in JP 2020-172574 A.

[0046] The epoxy equivalent of the epoxy resin is preferably 50 to 5,000 g / eq, more preferably 50 to 3,000 g / eq, even more preferably 60 to 2,000 g / eq, particularly preferably 70 to 1,000 g / eq, and most preferably 100 to 500 g / eq. The epoxy equivalent refers to the mass of a resin containing one equivalent of epoxy groups, and can be measured according to JIS K7236. The lower limit of the viscosity of the epoxy resin is preferably 500 mPa·s or more. The upper limit is not particularly limited, but is, for example, 100 Pa·s or less, preferably 5000 mPa·s or less, more preferably 4000 mPa·s or less, and even more preferably 3000 mPa·s or less. Here, the viscosity of the epoxy resin is a value measured using an E-type viscometer at 25±2°C.

[0047] The lower limit of the weight average molecular weight of the epoxy resin is preferably 100 or more, more preferably 250 or more, and even more preferably 400 or more. The upper limit is preferably 5000 or less, more preferably 3000 or less, and even more preferably 1500 or less.

[0048] The epoxy resins may be used alone or in combination of two or more. The lower limit of the epoxy resin content (the total content when multiple epoxy resins are included) is preferably 3% by mass or more, more preferably 5% by mass or more, based on the total solid content in the composition, and the upper limit is preferably 20% by mass or less, more preferably 15% by mass or less, based on the total solid content in the composition. The lower limit of the epoxy resin content (the total content when multiple epoxy resins are included) is preferably 3% by mass or more, more preferably 5% by mass or more, relative to the total mass of the composition, and the upper limit is preferably 20% by mass or less, more preferably 15% by mass or less, relative to the total mass of the composition.

[0049] [Reactive Diluent] The composition may also include a reactive diluent. The composition generally has a high viscosity due to the large amount of specific magnetic particles contained therein. When the composition contains a reactive diluent, the viscosity of the composition can be reduced, resulting in better compressibility of the composition. The reactive diluent is a compound having a reactive group, and examples of the reactive group include an epoxy group, an acryloyl group, a methacryloyl group, and an oxetane group. Of these, the epoxy group is preferred as the reactive group. The reactive diluent containing an epoxy group does not include those corresponding to the above-mentioned epoxy resins. The number of reactive groups in the reactive diluent is not particularly limited, but is, for example, 1 or more, and more preferably 2 or more. The upper limit is not particularly limited, but is, for example, 10 or less, and preferably 6 or less. The viscosity of the reactive diluent is preferably 1 mPa·s or more and less than 500 mPa·s, more preferably 5 mPa·s or more and less than 500 mPa·s, and even more preferably 10 mPa·s or more and less than 500 mPa·s. The viscosity of the reactive diluent can be measured in the same manner as the viscosity of the epoxy resin described above.

[0050] Commercially available reactive diluents include, for example, "EX-201" (alicyclic glycidyl ether), "EX-830" and "EX-821" (ethylene glycol-type epoxy resin), "EX-212" (hexanediol-type epoxy resin), and "ZX-1658" and "ZX-1658GS" (liquid 1,4-glycidylcyclohexane) manufactured by Nippon Steel Chemical & Material Co., Ltd.; "EP-3980S" (glycidylamine-type epoxy resin), "EP-4088S" and "EP-4088L" (dicyclopentadiene-type epoxy resin), "ED-523T" (neopentyl glycol glycidyl ether), and "ED-509S" (tert-butylphenyl glycidyl ether) manufactured by ADEKA Corporation; and "X-22-163" (siloxane-type epoxy resin) manufactured by Shin-Etsu Chemical Co., Ltd. In addition to the reactive diluents described above, the Epochalic series "THI-DE", "DE-102", and "DE-103" (alicyclic epoxy compounds) manufactured by ENEOS Corporation, as well as the epoxy compounds described in JP 2020-172574 A can also be used as reactive diluents.

[0051] When the reactive diluent has an epoxy group, the epoxy equivalent of the reactive diluent is preferably 50 to 5000 g / eq., more preferably 50 to 3000 g / eq., still more preferably 60 to 2000 g / eq., and particularly preferably 70 to 1000 g / eq.

[0052] The reactive diluents may be used alone or in combination of two or more. When the composition contains a reactive diluent, the lower limit of the content of the reactive diluent (the total content when multiple reactive diluents are contained) is preferably 1% by mass or more, more preferably 2% by mass or more, based on the total solid content of the composition, and the upper limit is preferably 10% by mass or less, more preferably 8% by mass or less, and even more preferably 5% by mass or less. When the composition contains a reactive diluent, the lower limit of the content of the reactive diluent (the total content when multiple reactive diluents are contained) is preferably 1% by mass or more, more preferably 2% by mass or more, relative to the total mass of the composition, and the upper limit is preferably 10% by mass or less, more preferably 8% by mass or less, and even more preferably 5% by mass or less, relative to the total mass of the composition.

[0053] The ratio of the epoxy resin content to the reactive diluent content (epoxy resin content / reactive diluent content) is preferably 0.05 or more, more preferably 0.1 or more. There is no particular upper limit, but it is, for example, 5 or less, preferably 4 or less, more preferably 3 or less, and even more preferably 2.5 or less.

[0054] [Curing agent] The composition preferably includes a curing agent. The curing agent is not particularly limited, but examples thereof include phenol-based curing agents, naphthol-based curing agents, acid anhydride-based curing agents, imidazole-based curing agents, active ester-based curing agents, benzoxazine-based curing agents, cyanate ester-based curing agents, carbodiimide-based curing agents, and amine adduct-based curing agents.

[0055] Specific examples of phenol-based curing agents and naphthol-based curing agents include "MEH-7700," "MEH-7810," and "MEH-7851" manufactured by Meiwa Chemical Industry Co., Ltd.; "NHN," "CBN," and "GPH" manufactured by Nippon Kayaku Co., Ltd.; "SN-170," "SN-180," "SN-190," "SN-475," "SN-485," "SN-495," "SN-375," and "SN-395" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.; and "LA-7052," "LA-7054," "LA-3018," "LA-3018-50P," "LA-1356," "TD2090," and "TD-2090-60M" manufactured by DIC Corporation.

[0056] Acid anhydride curing agents include curing agents having one or more acid anhydride groups in one molecule. Specific examples of acid anhydride curing agents include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, hydrogenated methylnadic anhydride, trialkyltetrahydrophthalic anhydride, dodecenyl succinic anhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trimellitic anhydride, pyromellitic anhydride, and benzophenonetetracarboxylic acid dianhydride. Examples of suitable anhydrides include ethylene glycol bis(anhydrotrimellitate), ethylene glycol bis(anhydrotrimellitate), and polymeric anhydrides such as styrene-maleic acid resins, which are copolymers of styrene and maleic acid. Commercially available acid anhydride curing agents include "HNA-100," "MH-700," "MTA-15," "DDSA," "HF-08," and "OSA" manufactured by New Japan Chemical Co., Ltd.; "YH306" and "YH307" manufactured by Mitsubishi Chemical Corporation; "H-TMAn" manufactured by Mitsubishi Gas Chemical Company, Inc.; and "HN-2200," "HN-2000," "HN-5500," and "MHAC-P" manufactured by Hitachi Chemical Co., Ltd.

[0057] As the active ester curing agent, a compound having three or more highly reactive ester groups in one molecule, such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds, is preferably used. The active ester curing agent is preferably an active ester compound containing a dicyclopentadiene-type diphenol structure, an active ester compound containing a naphthalene structure, an active ester compound containing an acetylated product of phenol novolac, or an active ester compound containing a benzoylated product of phenol novolac. Note that the "dicyclopentadiene-type diphenol structure" refers to a divalent structural unit consisting of phenylene-dicyclopentalene-phenylene.

[0058] Imidazole-based curing agents include 2-methylimidazole (trade name: 2MZ), 2-undecylimidazole (trade name: C11-Z), 2-heptadecylimidazole (trade name: C17Z), 1,2-dimethylimidazole (trade name: 1.2DMZ), 2-ethyl-4-methylimidazole (trade name: 2E4MZ), 2-phenylimidazole (trade name: 2PZ), 2-phenyl-4-methylimidazole (trade name: 2P4MZ), and 1-benzyl-2-methylimidazole (trade name: 1B2MZ). ), 1-benzyl-2-phenylimidazole (trade name: 1B2PZ), 1-cyanoethyl-2-methylimidazole (trade name: 2MZ-CN), 1-cyanoethyl-2-undecylimidazole (trade name: C11Z-CN), 1-cyanoethyl-2-phenylimidazolium trimellitate (trade name: 2PZCNS-PW), 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine (trade name: 2MZ-A), 2,4-diamino-6-[2'-undecyli midazolyl-(1')]-ethyl-s-triazine (trade name: C11Z-A), 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-s-triazine (trade name: 2E4MZ-A), 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine isocyanuric acid adduct (trade name: 2MA-OK), 2-phenyl-4,5-dihydroxymethylimidazole (trade name: 2PHZ-PW), 2-phenyl-4-methyl-5-hydroxy ... Examples of imidazole-based curing agents include 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine (trade name: 2MZA-PW), and 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine isocyanuric acid adduct (trade name: 2MAOK-PW) (all manufactured by Shikoku Chemicals Corporation).

[0059] Commercially available active ester curing agents include "EXB9451," "EXB9460," "EXB9460S," "HPC-8000," "HPC-8000H," "HPC-8000-65T," "HPC-8000H-65TM," "EXB-8000L," and "EXB-8000L-65TM" (manufactured by DIC Corporation) as active ester compounds containing a dicyclopentadiene-type diphenol structure; "EXB9416-70BK" and "EXB-8150-65T" (manufactured by DIC Corporation) as active ester compounds containing a naphthalene structure; and "EXB9416-70BK" and "EXB-8150-65T" (manufactured by DIC Corporation) as active ester compounds containing a naphthalene structure. Examples of active ester compounds containing acetylated phenol novolac include "DC808" (manufactured by Mitsubishi Chemical Corporation); active ester compounds containing benzoated phenol novolac include "YLH1026" (manufactured by Mitsubishi Chemical Corporation); active ester curing agents that are acetylated phenol novolac include "DC808" (manufactured by Mitsubishi Chemical Corporation); and active ester curing agents that are benzoated phenol novolac include "YLH1026" (manufactured by Mitsubishi Chemical Corporation), "YLH1030" (manufactured by Mitsubishi Chemical Corporation), and "YLH1048" (manufactured by Mitsubishi Chemical Corporation).

[0060] Specific examples of benzoxazine curing agents include "JBZ-OP100D" and "ODA-BOZ" manufactured by JFE Chemical Corporation; "HFB2006M" manufactured by Showa Polymer Co., Ltd.; and "Pd" and "Fa" manufactured by Shikoku Chemical Industry Co., Ltd.

[0061] Specific examples of cyanate ester curing agents include "PT30" and "PT60" manufactured by Lonza Japan Ltd. (both are phenol novolac type multifunctional cyanate ester resins), as well as "BA230" and "BA230S75" (prepolymers in which part or all of bisphenol A dicyanate has been triazine converted to a trimer).

[0062] Specific examples of carbodiimide curing agents include "V-03" and "V-07" manufactured by Nisshinbo Chemical Inc.

[0063] Commercially available amine adduct curing agents include, for example, "PN-23" and "PN-50" from the Amicure series (both manufactured by Ajinomoto Fine-Techno Co., Ltd.).

[0064] The curing agent may be used alone or in combination of two or more kinds. When the composition contains a curing agent, the content of the curing agent (the total content when multiple curing agents are contained) is preferably 0.001 to 3 mass %, more preferably 0.01 to 2 mass %, based on the total solid content of the composition. When the composition contains a curing agent, the content of the curing agent (the total content when multiple curing agents are contained) is preferably 0.001 to 3 mass %, more preferably 0.01 to 2 mass %, based on the total mass of the composition.

[0065] [Curing accelerator] The curing accelerator is not particularly limited, but examples thereof include triphenylphosphine, methyltributylphosphonium dimethylphosphate, trisorthotolylphosphine, and boron trifluoride amine complex. An example of a commercially available phosphate curing accelerator is Hishicolin PX-4MP (manufactured by Nippon Chemical Industry Co., Ltd.). Further, examples of triarylphosphine-based curing accelerators include the compounds described in paragraph 0052 of JP-A No. 2004-043405. Examples of phosphorus-based curing accelerators in which triphenylborane is added to triarylphosphine include the compounds described in paragraph 0024 of JP-A No. 2014-005382.

[0066] The curing accelerator may be used alone or in combination of two or more kinds. When the composition contains a curing accelerator, the content of the curing accelerator (when multiple curing accelerators are contained, the total content) is preferably 0.001 to 3 mass %, more preferably 0.01 to 2 mass %, based on the total solid content of the composition. When the composition contains a curing accelerator, the content of the curing accelerator (when multiple curing accelerators are contained, the total content) is preferably 0.001 to 3 mass %, more preferably 0.01 to 2 mass %, relative to the total mass of the composition.

[0067] [Dispersant] Preferably, the composition further comprises a dispersant. Examples of dispersants include phosphate ester dispersants such as polyoxyethylene alkyl ether phosphate; anionic dispersants such as sodium dodecylbenzelsulfonate, sodium laurate, and ammonium salts of polyoxyethylene alkyl ether sulfate; organosiloxane dispersants; and nonionic dispersants such as acetylene glycol, polyoxyethylene alkyl ether, polyoxyethylene alkyl ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene alkylphenyl ether, polyoxyethylene alkylamine, and polyoxyethylene alkylamide. When a resin has an epoxy group, it is included in the above-mentioned epoxy resin. The dispersant may be used alone or in combination of two or more kinds. Commercially available phosphate ester dispersants include, for example, "RS-410," "RS-610," and "RS-710" from the "Phosphanol" series manufactured by Toho Chemical Industry Co., Ltd. Commercially available organosiloxane dispersants include "BYK347" and "BYK348" manufactured by BYK-Chemie. Commercially available polyoxyalkylene dispersants include "AKM-0531," "AFB-1521," "SC-0505K," "SC-1015F," "SC-0708A," and "HKM-50A" from the "Marialim" series manufactured by NOF Corporation. The polyoxyalkylene dispersant is a general term that includes polyoxyethylene alkyl ethers, polyoxyethylene alkyl esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene alkylphenyl ethers, polyoxyethylene alkylamines, polyoxyethylene alkylamides, and the like. Commercially available acetylene glycol products include "82," "104," "440," "465," and "485" from the "Surfynol" series manufactured by Air Products and Chemicals Inc., as well as "Olefin Y."

[0068] The dispersant may be used alone or in combination of two or more kinds. When the composition contains a dispersant, the content of the dispersant (the total content when multiple dispersants are contained) is preferably 0.001 to 3 mass %, more preferably 0.01 to 2 mass %, based on the total solid content of the composition. When the composition contains a dispersant, the content of the dispersant (the total content when multiple dispersants are contained) is preferably 0.001 to 3 mass %, more preferably 0.01 to 2 mass %, relative to the total mass of the composition.

[0069] 〔solvent〕 The composition may include a solvent. When the composition contains a solvent, the content of the solvent is preferably 1% by mass or less, more preferably 0.8% by mass or less, and even more preferably 0.5% by mass or less, relative to the total mass of the composition. The lower limit is not particularly limited, but is at least 0.001% by mass.

[0070] [Other optional ingredients] The composition may further contain other optional components in addition to the components described above, such as magnetic particles other than the specific magnetic particles, a polymerization initiator, a polymerizable compound other than a reactive diluent, a surfactant, a rheology control agent, a resin other than an epoxy resin (e.g., an alkali-soluble resin), a sensitizer, a co-sensitizer, a plasticizer, an oil-sensitizing agent, a filler, and a rubber component, and further known additives such as auxiliaries (e.g., an antifoaming agent, a flame retardant, a leveling agent, a release accelerator, an antioxidant, a fragrance, a surface tension modifier, and a chain transfer agent) may be added as needed.

[0071] [Method for producing the composition] The composition can be prepared by mixing the above components by a known mixing method (for example, a mixing method using a stirrer, a homogenizer, a high-pressure emulsifier, a wet grinder, or a wet disperser). When preparing the composition, the components may be mixed all at once, or each component may be dissolved or dispersed in a solvent and then mixed successively. The order of addition and working conditions for mixing are not particularly limited. For example, when multiple types of other resins are used, they may be mixed all at once, or each type may be mixed in multiple batches.

[0072] [Application] The composition can be suitably used as a hole-filling composition for holes such as via holes and through holes provided in a circuit board. An example of a specific procedure for hole filling includes a method including the following steps 1 to 3. Step 1: A step of applying a composition to a substrate having holes such as via holes or through holes by a known application method such as slit coating, ink jetting, spin coating, casting, roll coating, or screen printing to fill the holes with the composition. Step 2: A step of curing the thermosetting components (e.g., epoxy resin and reactive diluent) in the composition by heating the composition on the substrate that has been subjected to Step 1, for example, at about 120 to 180°C for about 30 to 90 minutes. Step 3: A step of removing unnecessary portions of the magnetic particle-containing cured material obtained in Step 2 that protrude from the substrate surface by physical polishing to form a flat surface. The circuit board containing the magnetic particle-containing cured material is suitable for use as an electronic component such as an antenna or inductor mounted in electronic communication equipment.

[0073] The composition is also preferably formed into a film. The thickness of the film formed from the composition is preferably 1 to 10,000 μm, more preferably 10 to 1,000 μm, and particularly preferably 15 to 800 μm, in terms of superior magnetic permeability. Films formed from the composition are suitable for use as electronic components such as antennas and inductors mounted in electronic communication devices and the like.

[0074] [Cured product containing magnetic particles] The magnetic particle-containing cured product of the present invention is a cured product formed from the above-described composition. The shape of the magnetic particle-containing cured product is not particularly limited, and may be, for example, a shape that matches the shape of the hole provided in the substrate, as described above, or may be in the form of a film. As an example of a specific embodiment of the method for producing a magnetic particle-containing cured material, the upper section describes a method for producing a magnetic particle-containing cured material when the composition is used as a hole-filling composition. Below, as an example of another specific embodiment, a method for producing a film-like magnetic particle-containing cured material (hereinafter also referred to as a "magnetic particle-containing film") will be described.

[0075] [Method for producing a magnetic particle-containing film] The magnetic particle-containing film can be obtained by curing the above-mentioned composition. The method for producing a magnetic particle-containing film is not particularly limited, but is preferably a production method including the following steps: When carrying out the following method for producing a magnetic particle-containing film, it is also preferable that the composition contains a cationic polymerization initiator that responds to light and / or heat. ·Composition layer formation process ·Curing process

[0076] <Composition layer formation process> In the composition layer forming step, a composition layer (composition layer) is formed by applying the composition onto a substrate (support) etc. The substrate may be, for example, a wiring board having an antenna part or an inductor part.

[0077] The composition can be applied to a substrate by various coating methods, such as slit coating, inkjet coating, spin coating, casting coating, roll coating, and screen printing. The film thickness of the composition layer is preferably 1 to 10,000 μm, more preferably 10 to 1,000 μm, and even more preferably 15 to 800 μm. The composition layer applied to the substrate may be heated (prebaked). Prebaking can be performed, for example, on a hot plate or in an oven at a temperature of 50 to 140° C. for 10 to 1,800 seconds. Prebaking is preferably performed when the composition contains a solvent.

[0078] <Curing process> The curing step is not particularly limited as long as it can cure the composition layer, and examples thereof include a heat treatment for heating the composition layer and an exposure treatment for irradiating the composition layer with actinic rays or radiation.

[0079] When heat treatment is carried out, the heat treatment can be carried out continuously or batchwise using a heating means such as a hot plate, a convection oven (hot air circulation dryer), or a high-frequency heater. The heating temperature in the heat treatment is preferably 120 to 260° C., more preferably 150 to 240° C. The heating time is not particularly limited, but is preferably 10 to 1800 seconds. The pre-baking in the composition layer forming step may also serve as the heat treatment in the curing step.

[0080] When exposure treatment is carried out, the method of irradiating with actinic rays or radiation is not particularly limited, but it is preferable to irradiate through a photomask having patterned openings. The exposure is preferably carried out by irradiation with radiation. The radiation that can be used for exposure is preferably ultraviolet light such as g-ray, h-ray, or i-ray, and the light source is preferably a high-pressure mercury lamp. The irradiation intensity is 5 to 1500 mJ / cm. 2 is preferred, and 10 to 1000 mJ / cm 2 is more preferred. When the composition contains a thermal polymerization initiator, the composition layer may be heated during the exposure treatment. The heating temperature is not particularly limited, but is preferably 80 to 250° C. The heating time is not particularly limited, but is preferably 30 to 300 seconds. In addition, when the composition layer is heated in the exposure treatment, this may also serve as a post-heating step described below. In other words, when the composition layer is heated in the exposure treatment, the method for producing a magnetic particle-containing film does not need to include a post-heating step.

[0081] <Developing process> When an exposure treatment is performed in the curing step, a development step may be further included. The development step is a step of developing the composition layer after exposure to form a magnetic particle-containing film. By this step, the composition layer in the unexposed areas is eluted, leaving only the photocured areas, thereby obtaining a patterned magnetic particle-containing film. The type of developer used in the development step is not particularly limited, but an alkaline developer that does not damage circuits and the like is desirable. The development temperature is, for example, 20 to 30°C. The developing time is, for example, 20 to 90 seconds. In recent years, the developing time may be extended to 120 to 180 seconds to more effectively remove residues. Furthermore, to further improve residue removal, the developer may be shaken off every 60 seconds and new developer may be supplied, and this process may be repeated several times.

[0082] The alkaline developer is preferably an alkaline aqueous solution prepared by dissolving an alkaline compound in water to a concentration of 0.001 to 10% by mass (preferably 0.01 to 5% by mass). Examples of alkaline compounds include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide, choline, pyrrole, piperidine, and 1,8-diazabicyclo[5.4.0]-7-undecene (among these, organic alkalis are preferred). When an alkaline developer is used, a washing treatment with water is generally carried out after development.

[0083] <Post-bake> When an exposure treatment is performed in the curing step, it is preferable to perform a heat treatment (post-bake) after the curing step. Post-bake is a heat treatment to complete the curing. When a development step is performed, it is preferable to perform post-bake after the development step. The heating temperature is preferably 240°C or less, more preferably 220°C or less. There is no particular lower limit, but in consideration of efficient and effective treatment, it is preferably 50°C or more, more preferably 100°C or more. Furthermore, the heating time is not particularly limited, but is preferably 10 to 1800 seconds. Post-baking can be carried out continuously or batchwise using a heating means such as a hot plate, a convection oven (hot air circulation dryer), or a high-frequency heater.

[0084] The post-baking is preferably carried out in an atmosphere with a low oxygen concentration. The oxygen concentration is preferably 19% by volume or less, more preferably 15% by volume or less, even more preferably 10% by volume or less, particularly preferably 7% by volume or less, and most preferably 3% by volume or less. There is no particular lower limit, but a practical value is 10 ppm by volume or more.

[0085] [Electronic Components] The electronic component of the present invention includes the above-described magnetic particle-containing cured material. That is, the electronic component of the present invention may include the above-described magnetic particle-containing cured material as a part of the component. Examples of the electronic component include an inductor and an antenna. The electronic component may have a known structure. [Example]

[0086] The present invention will be described in more detail below with reference to the following examples. The materials, amounts used, ratios, treatment details, treatment procedures, etc. shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the following examples. In the following description, unless otherwise specified, "%" means "% by mass" and "parts" means "parts by mass".

[0087] [Various components used in preparing the composition] The components listed in the table below were prepared for the preparation of the compositions. The outline of each component listed in the table is shown below.

[0088] [Magnetic particles] The magnetic particles used were P-1 to P-4 and CP-1 to CP-4 shown below. P-1: Product name "KUAMET NC1" (manufactured by Epson Atmix Corporation) "Fe nanocrystalline alloy, Fe atom content: 83 mass%, D50: 16 μm, solid content: 100 mass%" P-2: Product name "KUAMET NC1" (manufactured by Epson Atmix Corporation) "Fe nanocrystalline alloy, Fe atom content: 83 mass%, D50: 23 μm, solid content: 100 mass%" P-3: Product name "KUAMET6B2-53μm" (Epson Atmix Corporation) "Fe-based amorphous, Fe atom content: 87% by mass, D50: 24μm, solid content: 100% by mass" P-4: Product name "EA-SMP-10 PF-20F" (manufactured by Epson Atmix Corporation) "FeSiCr alloy, Fe atom content: 92% by mass, D50: 10 μm, solid content: 100% by mass"

[0089] CP-1: Fe-Mn ferrite manufactured by Powder Tech Co., Ltd. "Fe-Mn ferrite, D50: 3 μm, solid content: 100% by mass" CP-2: Fe-Mn ferrite manufactured by Powder Tech Co., Ltd. "Fe-Mn ferrite, D50: 0.2 μm, solid content: 100% by mass" CP-3: Product name "AW2-08 PF3F" (Epson Atmix Corporation) "Fe-based amorphous, Fe atom content: 87% by mass, D50: 3 μm, solid content: 100% by mass" CP-4: Product name "KUAMET6B2-150μm" (Epson Atmix Corporation) "Fe-based amorphous, Fe atom content: 87% by mass, D50: 50μm, solid content: 100% by mass"

[0090] 〔resin〕 <Epoxy resin> D-1: Product name "ZX-1059" (manufactured by Nippon Steel Chemical & Material Co., Ltd.) "Liquid epoxy resin (a mixture of bisphenol A epoxy resin and bisphenol F epoxy resin), solid content: 100% by mass" D-3: Product name "EPICLON N-695" (manufactured by DIC Corporation) "Cresol novolac epoxy resin, solid content: 100% by mass" D-4: Product name "EHPE 3150" (manufactured by Daicel Chemical Industries, Ltd.) "alicyclic epoxy resin, solid content: 100% by mass" <Dispersant> D-2: Product name "RS-710" (manufactured by Toho Chemical Industry Co., Ltd.) "Phosphate ester dispersant, solid content: 100% by mass"

[0091] [Curing agent] A-1: Product name "2MZA-PW" (manufactured by Shikoku Chemicals Corporation) "Imidazole-based curing accelerator, solid content: 100% by mass" A-2: Product name "LA-7054" (DIC Corporation) "Triazine skeleton-containing phenolic curing agent, solid content: 100% by mass"

[0092] [Reactive Diluent] C-1: Product name "ZX-1658GS" (manufactured by Nippon Steel Chemical & Material Co., Ltd.) "Cyclic aliphatic diglycidyl ether, solid content: 100% by mass" C-2: Product name "EX-201" (Nagase ChemteX Corporation) "Resorcinol diglycidyl ether, solid content: 100% by mass" C-3: Product name "ED-523T" (ADEKA Corporation) "Low viscosity epoxy resin, solid content: 100% by mass"

[0093] [Preparation of compositions of examples and comparative examples] The components shown in the table below were mixed and uniformly dispersed in a roll mill to prepare compositions for each of the Examples and Comparative Examples.

[0094] [Various measurements and evaluations] 〔measurement〕 <Measurement of peak top Dmax and Dmin> For each composition of the Examples and Comparative Examples, a particle size distribution curve representing a volume-based frequency distribution was measured based on the method described above, and the Dmax (μm), Dmin (μm), and Dmax / Dmin of the magnetic particles contained in each composition of the Examples and Comparative Examples were determined. When the number of peak tops in the particle size distribution curve representing the volume-based frequency distribution is one, the particle size at which the peak top appears is shown in the table below as Dmax.

[0095] 〔evaluation〕 <Magnetic performance evaluation (magnetic permeability, magnetic loss)> Using an applicator, each composition of the Examples and Comparative Examples was applied onto a Si wafer having a thickness of 100 μm so that the film thickness after formation would be 100 μm, thereby forming a coating film. Next, the substrate was heated and dried at 100° C. for 10 minutes, and then further heated at 230° C. for 10 minutes to produce a substrate with a cured film. The obtained substrates with cured films were then cut into pieces measuring 1 cm × 2.8 cm, and the permeability of the cured films on each of the obtained measurement sample substrates was measured at 50 MHz using PER-01 (a high-frequency permeability measuring device manufactured by Keycom Corporation), to obtain the complex relative permeability μ' (real part) and μ'' (imaginary part) of the cured films.

[0096] In addition, the magnetic loss (tan δ) was calculated based on the following formula (1). Equation (1): tanδ=μ'' / μ'

[0097] The obtained value of relative magnetic permeability μ' was evaluated based on the following evaluation criteria, and this was taken as the evaluation result of magnetic permeability. In practice, relative magnetic permeability μ' is preferably rated "B" or higher.

[0098] (Evaluation criteria for relative permeability μ') "A": 10≦μ' "B": 5≦μ'<10 "C": μ'<5

[0099] The obtained magnetic loss (tan δ) values ​​were evaluated based on the following evaluation criteria: In practice, the magnetic loss (tan δ) evaluation result is preferably "B" or higher. (Evaluation criteria for magnetic loss (tanδ)) "A": tanδ≦0.1 "B": 0.1 <tanδ≦0.25 "C": 0.25 <tanδ

[0100] <Embedding suitability evaluation> A 0.8 mm thick FR-4 substrate was prepared, and a through hole with a diameter of 0.4 mm was formed. Next, each composition of the Examples and Comparative Examples was embedded in the through-holes using a DP-320 (Newlong Precision Industry Co., Ltd.), and the resulting embedded substrate was heated at 160°C for 1 hour to harden the composition. The obtained substrate was polished to expose the cross section of the buried portion, and the internal state was observed using a SEMS (scanning electron microscope). Thirty images were taken, and the void ratios calculated using Image J were averaged to provide an index of embeddability. The value (Va) obtained by averaging was used to evaluate the embeddability in accordance with the following evaluation criteria. The smaller the Va value, the fewer voids and cracks there were in the cured product, which is better. In practical terms, an evaluation result of "B" or higher is preferable for embeddability.

[0101] (Evaluation criteria for embeddability) "A": Va<5% "B": 5%≦Va<15% "C": 15%≦Va

[0102] The following table shows the formulation of each composition and the results of the evaluation tests carried out on each composition. In the following table, when the particle size distribution curve representing the volume-based frequency distribution has one peak top, the particle size at which the peak top appears is recorded as Dmax.

[0103] [Table 1]

[0104] From the results in the above table, it is clear that the compositions of the examples provide cured products with high magnetic permeability and low magnetic loss. It is also clear that the compositions of the examples have excellent embeddability. Furthermore, a comparison of Examples 1 to 4 confirmed that magnetic loss was smaller when the specific magnetic particles in the composition had a peak top at 10 to 20 μm in the particle size distribution curve representing the volume-based frequency distribution. Furthermore, a comparison of Examples 1 to 4 confirmed that the magnetic permeability was higher when the specific magnetic particles in the composition had a peak top in the range of 12 to 30 μm in the particle size distribution curve representing the volume-based frequency distribution. Furthermore, a comparison of Examples 1, 3, 5, and 6 confirmed that magnetic loss is smaller when the specific magnetic particles in the composition have a Dmax in the range of 10 to 30 μm and a Dmin in the range of 1 to 9 μm in the particle size distribution curve representing the volume-based frequency distribution. Furthermore, a comparison between Examples 5 and 7 confirmed that the magnetic permeability is higher when the specific magnetic particles in the composition exhibit a Dmax / Dmin of 2 or more in the particle size distribution curve representing the volume-based frequency distribution. Comparing Example 1 and Example 13, it was confirmed that the magnetic permeability was higher when the content of the specific magnetic particles was 75 to 90 mass %.

[0105] On the other hand, the compositions of the comparative examples did not provide the desired effects. [Explanation of symbols]

[0106] P, Pmin, Pmax peak top Dmin, Dmax particle size

Claims

1. A composition comprising magnetic particles containing 70% by mass or more of Fe atoms and an epoxy resin, the magnetic particles have a peak top in the range of 10 to 30 μm in a particle size distribution curve representing a volume-based frequency distribution; the magnetic particles have a plurality of peak tops in a particle size distribution curve representing the volume-based frequency distribution, the magnetic particles include magnetic particles made of a material containing an amorphous alloy and magnetic particles made of a material containing a non-amorphous alloy, A composition in which the content of the magnetic particles is 70 to 90 mass % based on the total solid content of the composition.

2. A composition comprising magnetic particles containing 70% by mass or more of Fe atoms and an epoxy resin, the magnetic particles have a peak top in the range of 10 to 30 μm in a particle size distribution curve representing a volume-based frequency distribution; the number of peak tops in the particle size distribution curve representing the volume-based frequency distribution is one, the content of the magnetic particles is 70 to 90 mass % based on the total solid content of the composition, The composition, wherein the material constituting the magnetic particles is an Fe-based amorphous alloy, an Fe nanocrystalline alloy, or an Fe—Ni—Co alloy.

3. 3. The composition according to claim 1, wherein the magnetic particles contain 70 to 95 mass % Fe atoms.

4. 2. The composition according to claim 1, wherein, when the particle diameter at the peak top Pmin having the smallest particle diameter among the plurality of peak tops is defined as Dmin and the particle diameter at the peak top Pmax having the largest particle diameter is defined as Dmax / Dmin is 2 or more.

5. The composition of claim 4, wherein the Dmax is in the range of 10 to 30 μm and the Dmin is in the range of 1 to 9 μm.

6. The composition according to any one of claims 1 to 5, further comprising a reactive diluent.

7. The composition according to any one of claims 1 to 6, further comprising a curing agent.

8. A magnetic particle-containing cured product formed using the composition according to any one of claims 1 to 7.

9. An electronic component comprising the magnetic particle-containing cured product according to claim 8 .

10. The electronic component according to claim 9, which is used as an inductor.

11. The electronic component according to claim 10, which is used as an antenna.

Citation Information

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