WO2020217476A1

WO2020217476A1 - Compound, molded article, hardened product of compound, and method for manufacturing compound

Info

Publication number: WO2020217476A1
Application number: PCT/JP2019/018020
Authority: WO
Inventors: 須田　聡一郎; 稲垣　孝; 石原　千生; 竹内　一雅
Original assignee: 日立化成株式会社
Priority date: 2019-04-26
Filing date: 2019-04-26
Publication date: 2020-10-29
Also published as: JP7231017B2; KR102623788B1; KR20220003504A; JP2023054087A; JPWO2020217476A1; KR20240008976A; CN113728403A; JP2024040258A

Abstract

This compound comprises a metal filler containing a first metal powder, and a resin composition. The first metal powder contains a plurality of first metal particles, at least some of the surface of the first metal particles being covered by glass that contains Si, and the median diameter in the first metal powder being 1.0 to 5.0 µm [inclusive].

Description

Compounds, molded articles, cured products of compounds, and methods for manufacturing compounds

The present invention relates to a compound, a molded product, a cured product of the compound, and a method for producing the compound.

The compound containing the metal powder and the resin composition is used as a raw material for various industrial products according to various physical properties of the metal powder. For example, the compound is used as a raw material for inductors, encapsulants, electromagnetic wave shields (EMI shields), bond magnets, and the like. (See Patent Document 1 below.)

Japanese Unexamined Patent Publication No. 2014-13803

When manufacturing an industrial product from a compound, the compound is supplied and filled in the mold, and parts such as coils are embedded in the compound. The fluidity of the compound is required in these steps. However, conventional compounds do not have sufficient liquidity. As the particle size of the metal powder decreases, the fluidity of the compound tends to decrease.

An object of the present invention is to provide a compound having excellent fluidity, a molded product containing the compound, a cured product of the compound, and a method for producing the compound.

The compound according to one aspect of the present invention comprises a metal filler containing a first metal powder and a resin composition, wherein the first metal powder contains a plurality of first metal particles and is on the surface of the first metal particles. At least a part thereof is covered with glass containing Si, and the median diameter of the first metal powder is 1.0 μm or more and 5.0 μm or less.

The first metal powder may be an alloy containing Fe.

The first metal particles may be spherical.

The resin composition may contain a thermosetting resin.

The compound according to one aspect of the present invention may be a powder or a paste.

The content of the metal filler in the compound may be 90% by mass or more and less than 100% by mass.

The metal filler may further contain the second metal powder, and the median diameter of the second metal powder may be larger than the median diameter of the first metal powder.

The median diameter of the second metal powder may be 20.0 μm or more and 30.0 μm or less, the mass of the first metal powder may be M1, and the mass of the second metal powder may be M2. 100 × M1 / (M1 + M2) may be 5 or more and 30 or less, and 100 × M2 / (M1 + M2) may be 70 or more and 95 or less.

The second metal powder may be an alloy containing Fe.

The secondary metal particles contained in the secondary metal powder may be spherical.

The D90 of the second metal powder may be 40 μm or more and 65 μm or less.

The molded product according to one aspect of the present invention includes the above compound.

The cured product of the compound according to one aspect of the present invention is the cured product of the above-mentioned compound.

The method for producing a compound according to one aspect of the present invention is the method for producing the above-mentioned compound, which comprises a step of obtaining a first mixture by mixing a metal filler and a clotting agent, and a resin composition excluding the clotting agent. A step of obtaining a second mixture by kneading the first mixture while heating, a step of obtaining a solid substance by cooling the second mixture, and a step of crushing the solid substance are provided. ..

The method for producing a compound according to another aspect of the present invention is a method for producing the above-mentioned compound, which comprises a step of obtaining a metal filler by mixing a first metal powder and a second metal powder, and a metal filler. The step of obtaining the first mixture by mixing the clotting agent, the step of obtaining the second mixture by kneading the resin composition excluding the clotting agent and the first mixture while heating, and the second. It includes a step of obtaining a solid substance by cooling the mixture and a step of crushing the solid substance.

According to the present invention, a compound having excellent fluidity, a molded product containing the compound, a cured product of the compound, and a method for producing the compound are provided.

Hereinafter, preferred embodiments of the present invention will be described. The present invention is not limited to the following embodiments.

The compound according to the present embodiment includes a metal filler containing the first metal powder and a resin composition. The metal filler may be paraphrased as the whole metal powder contained in the compound. The first metal powder contains a plurality of first metal particles. That is, the first metal powder means the whole of a plurality of first metal particles. At least a part of the surface of the first metal particles is covered with glass containing Si (silicon). For example, at least a part of the surface of the first metal particles may be covered with a glass film or a glass layer. The glass film or glass layer may be composed of a large number of glass particles containing Si. The compound may further comprise at least one other metal powder in addition to the primary metal powder. The resin composition may cover the surface of each metal particle constituting the metal filler. The resin composition may be present between the metal fillers, and the metal fillers may be attached to each other via the resin composition. The compound may further comprise a non-metallic filler (eg, silica or metal oxide).

As the particle size of each metal particle constituting the metal filler decreases, the gap between the metal particles decreases. As the gap between the metal particles decreases, the filling rate (content) of the metal filler in the compound increases. As the filling rate of the metal filler increases, the relative magnetic permeability of the compound increases. On the other hand, as the particle size of the metal particles decreases, the specific surface area of each metal particle increases. As the specific surface area of the metal particles increases, the metal filler tends to aggregate and the fluidity of the compound is impaired. If the first metal particles are not covered with glass, the first metal powder having a relatively small median diameter is particularly liable to agglomerate, and the agglomeration of the first metal powder tends to impair the fluidity of the compound. However, by covering the surface of the first metal particles with glass, the aggregation of the first metal powder is suppressed and the frictional force acting between the first metal particles is reduced. As a result, the decrease in the fluidity of the compound due to the small median diameter of the first metal powder is suppressed. In other words, by covering the surface of the first metal particles with glass, it is possible to suppress a decrease in the fluidity of the compound due to an increase in the filling rate of the metal filler.

The higher the coverage of the glass on the surface of the first metal particles, the more difficult it is for the first metal powder to aggregate, the easier it is for the frictional force acting between the first metal particles to be reduced, and the easier it is for the fluidity of the compound to improve. Therefore, the entire surface of the first metal particles may be covered with glass containing Si. However, only a part of the surface of the first metal particles may be covered with glass containing Si. Since the first metal powder is less likely to aggregate and the fluidity of the compound is likely to be improved, the surface of all the first metal particles contained in the first metal powder may be covered with glass containing Si. However, only the surface of some of the first metal particles contained in the first metal powder may be covered with glass containing Si.

The metal filler may contain at least one other metal powder having a median diameter different from that of the first metal powder, in addition to the first metal powder. For example, the metal filler may further contain a second metal powder in addition to the first metal powder. The secondary metal powder contains a plurality of secondary metal particles. That is, the secondary metal powder means the whole of the plurality of secondary metal particles. The median diameter of the second metal powder is larger than the median diameter of the first metal powder. If the compound contains only the second metal powder as the metal filler, gaps are likely to be formed between the second metal particles, and the filling rate of the metal filler in the compound is likely to decrease. On the other hand, when the compound contains the first metal powder and the second metal powder as the metal filler, the first metal particles smaller than the second metal particles are likely to be filled in the gaps formed between the second metal particles. As a result, the filling rate of the metal filler in the compound tends to increase. The relative magnetic permeability of the compound is likely to be controlled based on the mass ratio of the first metal powder and the second metal powder, and the relative magnetic permeability of the compound is likely to increase.

The surface of the second metal particles does not have to be covered with glass containing Si. At least a part of the surface of the second metal particles may be covered with glass containing Si. By covering the surface of the secondary metal particles with glass, the aggregation of the secondary metal powder is suppressed, and the decrease in the fluidity of the compound is suppressed. The entire surface of the second metal particles may be covered with glass containing Si. However, only a part of the surface of the second metal particles may be covered with glass containing Si. The surface of all the secondary metal particles contained in the secondary metal powder may be covered with glass containing Si. Only the surface of some of the secondary metal particles contained in the secondary metal powder may be covered with glass containing Si. All metal powders contained in the compound may be covered with glass containing Si.

The median diameter (D50) of the first metal powder is 1.0 μm or more and 5.0 μm or less, preferably 1.5 μm or more and 3.0 μm or less, and more preferably 2.17 μm or more and 2.31 μm or less. Since the fine first metal powder having D50 is contained in the compound, the filling rate of the metal filler in the compound tends to increase. If the D50 of the first metal powder is within the above range and the surface of the first metal particles is not covered with the crow film, the first metal powder tends to aggregate and the fluidity of the compound tends to decrease. .. However, by covering the surface of the first metal particles with glass, even when the D50 of the first metal powder is within the above range, the aggregation of the first metal powder is suppressed and the fluidity of the compound is lowered. Is suppressed. The D10 of the first metal powder may be, for example, 1.08 μm or more and 1.2 μm or less. The D90 of the first metal powder may be, for example, 3.88 μm or more and 4.43 μm or less. When D10 or D90 of the first metal powder is within the above range, the filling rate of the metal filler in the compound tends to increase. D10, D50 and D90 of the first metal powder may be calculated from the particle size distribution of the first metal powder based on the volume of the first metal powder. The particle size distribution of the first metal powder may be measured using, for example, a laser diffraction / scattering type particle size distribution measuring device. The particle size distribution of the primary metal powder may be measured before the primary metal powder is mixed with the other components of the compound. Each of D10, D50 and D90 of the first metal powder is a value including the thickness of the glass. The thickness of the glass may be significantly smaller than the particle size of the individual primary metal particles. For example, the scale of the thickness of the glass covering the first metal particles may be nanometers (nm).

The median diameter (D50) of the second metal powder may be 20.0 μm or more and 30.0 μm or less, preferably 22 μm or more and 28 μm or less, and more preferably 24.0 μm or more and 26.0 μm or less. When the fine second metal powder having D50 is contained in the compound, the filling rate of the metal filler in the compound tends to increase. The D10 of the second metal powder may be, for example, 6.0 μm or more and 12.0 μm or less. The D90 of the second metal powder may be, for example, 40 μm or more and 65 μm or less, preferably 45 μm or more and 65 μm or less. When D10 or D90 of the second metal powder is within the above range, the filling rate of the metal filler in the compound tends to increase. The secondary metal powders D10, D50 and D90 may be calculated from the particle size distribution of the secondary metal powder based on the volume of the secondary metal powder. The particle size distribution of the second metal powder may be measured using, for example, a laser diffraction / scattering type particle size distribution measuring device. The particle size distribution of the secondary metal powder may be measured before the secondary metal powder is mixed with the other components of the compound. When the second metal powder is covered with glass, D10, D50 and D90 of the second metal powder are values including the thickness of the glass. The thickness of the glass may be significantly smaller than the particle size of the individual secondary metal particles. For example, the scale of the thickness of the glass covering the second metal powder may be nanometers (nm).

The mass of the first metal powder may be expressed as M1. The mass of the second metal powder may be expressed as M2. The D50 of the first metal powder is 1.0 μm or more and 5.0 μm or less (preferably 2.17 μm or more and 2.31 μm or less), and the D50 of the second metal powder is 20.0 μm or more and 30.0 μm or less (preferably 24). In the case of (0.0 μm or more and 26.0 μm or less), 100 × M1 / (M1 + M2) may be 5 or more and 30 or less, and 100 × M2 / (M1 + M2) may be 70 or more and 95 or less. When 100 × M1 / (M1 + M2) and 100 × M2 / (M1 + M2) are within the above ranges, the first metal particles are likely to be filled in the gaps formed between the second metal particles, and the metal filler in the compound. The filling rate tends to increase. As a result, the relative magnetic permeability of the compound tends to increase. For the same reason as described above, 100 × M1 / (M1 + M2) may be preferably 13 or more and 23 or less, and 100 × M2 / (M1 + M2) may be preferably 77 or more and 87 or less.

The glass covering the surface of the first metal particles contains at least Si. The glass containing Si may further contain at least one element selected from the group consisting of, for example, O (oxygen), B (boron), Na (sodium) and Al (aluminum). The glass may include, for example, SiO ₂ (silicic acid glass) or borosilicate glass. A large number of particles made of Si-containing glass may cover the surface of the first metal particles. The means for covering the surface of the first metal particles with the above glass may be, for example, a spray dryer. That is, the surface treatment liquid containing Si may be sprayed onto the first metal powder. The surface treatment liquid containing Si may be a liquid containing the glass itself or a liquid containing a raw material for the glass. The means for covering the surface of the first metal particles with the above glass may be an impregnation method. For example, the first metal powder may be immersed in a surface treatment liquid containing Si. The first metal powder to which the surface treatment liquid is attached may be heated if necessary.

The surface of the metal particles constituting the metal filler may be covered with a coupling agent. The surface of the first metal particles may be further covered with a coupling agent. However, the coupling agent that covers the metal filler does not correspond to glass containing Si. The first metal particles may further have a surface covered with a coupling agent as well as a surface covered with glass. As the coupling agent, a silane coupling agent is preferable. The compound may further include a metal powder having a surface covered with a coupling agent as a metal powder separate from the first metal powder. The compound may further comprise a metal powder having a surface treated with phosphoric acid (eg, organic phosphoric acid). For example, the compound may further comprise a metal powder having a phosphate-covered surface. The first metal particles may further have a surface treated with phosphoric acid as well as a surface covered with glass.

The first metal powder may contain, for example, at least one selected from the group consisting of elemental metals and alloys. The alloy may include at least one selected from the group consisting of solid solutions, eutectic and intermetallic compounds. The first metal powder may contain one kind of metal element or a plurality of kinds of metal elements. The metal element contained in the first metal powder may be, for example, a base metal element, a noble metal element, a transition metal element, or a rare earth element.

The metal elements contained in the first metal powder are, for example, iron (Fe), copper (Cu), titanium (Ti), manganese (Mn), cobalt (Co), nickel (Ni), zinc (Zn), aluminum ( Al), tin (Sn), chromium (Cr), barium (Ba), strontium (Sr), lead (Pb), silver (Ag), placeodymium (Pr), neodymium (Nd), samarium (Sm) and dysprosium ( It may be at least one selected from the group consisting of Dy). The first metal powder may contain an element other than the metal element. The first metal powder may contain, for example, oxygen (О), beryllium (Be), phosphorus (P), boron (B), or silicon (Si). The first metal powder may be a soft magnetic material or a ferromagnetic material.

The first metal powder may be an alloy containing Fe. The second metal powder may also be an alloy containing Fe. All metal fillers contained in the compound may be Fe-containing alloys. Since the compound has an alloy containing Fe as a metal filler, the compound can have a high relative magnetic permeability. Compounds with high relative permeability may be applied, for example, to inductors or EMI filters. The first metal powder may be an alloy containing Fe, Cr and Si. When the first metal powder is an alloy containing Fe, Cr and Si, rusting of the first metal powder is likely to be suppressed. Further, when the first metal powder is an alloy containing Fe, Cr and Si, core loss in a cured product of the compound (for example, a portion of the inductor other than the coil) is likely to be suppressed. For the same reason, the second metal powder may also be an alloy containing Fe, Cr and Si. For the same reason, all metal fillers contained in the compound may be alloys containing Fe, Cr and Si.

The composition of the alloy containing Fe is not limited to the above composition. For example, the first metal powder contains Fe (iron), Co (cobalt), Ni (nickel), Si (silicon), B (boron), P (phosphorus), C (carbon), element α and element β. It may include metal glass, and the element α may be at least one element selected from the group consisting of Nb (niobium) and Mo (molybdenum), and the element β is composed of Cr (chromium) and Zr (zyroxide). It may be at least one element selected from the group. The first metal powders are Fe—Si alloys, Fe—Si—Al alloys (Sendust), Fe—Ni alloys (Permalloy), Fe—Cu—Ni alloys (Permalloy), and Fe—Co alloys (Permalloy). It may contain at least one selected from the group consisting of permalloys).

The first metal powder may be Fe alone. The first metal powder may contain, for example, at least one of amorphous iron powder and carbonyl iron powder.

The first metal powder is Nd-Fe-B alloy (rare earth magnet), Sm-Co alloy (rare earth magnet), Sm-Fe-N alloy (rare earth magnet), and Al-Ni-Co alloy (alnico). A metal magnet consisting of at least one selected from the group consisting of magnets) may be included.

The second metal powder may contain at least one selected from the group consisting of the above-mentioned simple substances and compounds. The composition of the second metal powder may be the same as the composition of the first metal powder. The composition of the second metal powder may differ from the composition of the first metal powder. The metal filler may contain at least one other metal powder that differs in composition from the first metal powder and the second metal powder. Another metal powder may contain at least one selected from the group consisting of elemental metals and compounds described above.

The first metal powder may contain at least one of nanocrystals and amorphous metals. That is, the first metal particles constituting the first metal powder may contain at least one of nanocrystals and amorphous metals. The amorphous metal may be metallic glass. At least some of the first metal particles may be single crystals. At least some of the first metal particles may be polycrystalline. At least some of the first metal particles may be amorphous metals. When the first metal particles are amorphous metals, iron loss (cоre lоss) in a device (for example, an inductor) made from a compound is likely to be reduced.

The second metal powder may contain at least one of nanocrystals and amorphous metals. That is, the second metal particles constituting the second metal powder may contain at least one of nanocrystals and amorphous metal. The amorphous metal may be metallic glass. At least some of the second metal particles may be single crystals. At least some of the secondary metal particles may be polycrystalline. At least some of the secondary metal particles may be amorphous metals. When the second metal particles are amorphous metals, iron loss (cоre lоss) in a device (for example, an inductor) made from a compound is likely to be reduced.

At least some of the first metal particles may be substantially spherical. All primary metal particles may be substantially spherical. When the first metal particles are substantially spherical, the surface of the first metal particles is smooth. As a result, the frictional force acting between the metal fillers is likely to be reduced, and the fluidity of the compound is likely to be improved. For the same reason, at least some of the second metal particles may be substantially spherical. All secondary metal particles may be substantially spherical. For the same reason, all metal fillers contained in the compound may be substantially spherical. Whether or not the first metal particles are spherical can be determined based on the sphericality of the metal filler. The sphericity of the metal filler can be measured by a particle shape image analyzer. As the particle shape image analysis apparatus, for example, PITA-04 manufactured by Seishin Enterprise Co., Ltd. may be used. The sphericity of the metal filler is measured in a state where the metal filler is dispersed in purified water. By generating ultrasonic waves in water for a predetermined time (for example, 60 seconds), the metal filler is dispersed in the purified water. In the calculation of the sphericity of the metal filler, the influence of aggregates (secondary particles) of the metal filler may be eliminated by using a certain index. The shapes of the first metal particles and the second metal particles are not limited to spheres.

The content of the metal filler in the compound may be 90% by mass or more and less than 100% by mass, 93% by mass or more and 99.5% by mass or less, or 94% by mass or more and 99.5% by mass or less. As the content of the metal filler increases, the relative permeability of the compound tends to increase. On the other hand, as the content of the metal filler increases, the fluidity of the compound tends to decrease. However, even when the content of the metal filler is high, it is possible to achieve both high relative permeability and high fluidity by containing the first metal powder in the compound. The content of the metal filler in the compound can be rephrased as the filling rate of the metal filler in the compound. The filling rate of the metal filler in the compound can be rephrased as the space factor of the metal filler in the compound. The content of the resin composition in the compound is greater than 0% by mass and 10% by mass or less, 0.5% by mass or more and 7% by mass or less, and 0.5% by mass or more and 6% by mass or less with respect to the total mass of the compound. It may be there.

The resin composition may be a component that can include a resin, a curing agent, a curing accelerator, and an additive. The resin composition may be the remaining components (nonvolatile components) excluding the organic solvent and the metal filler. The additive may be a component of the rest of the resin composition excluding the resin, the curing agent and the curing accelerator. The additive is, for example, a coupling agent or a flame retardant. The resin composition may contain wax as an additive. The mixture of the above metal filler and the uncured resin composition corresponds to the compound. The compound may be a powder. The compound may be a tablet. The compound may be a paste. By molding the compound, a molded product containing the compound is formed. By curing the resin composition in the molded product, a cured product of the compound can be obtained. The resin compositions described below may be considered as uncured resin compositions contained in the compound.

The resin composition has a function as a binder for the metal filler, and imparts mechanical strength to the molded product and the cured product formed from the compound. For example, when the compound is molded at high pressure using a mold, the resin composition is filled between the metal fillers and binds the metal fillers together. By curing the resin composition in the molded product formed from the compound, the cured product of the resin composition firmly binds the metal fillers to each other.

The resin composition may contain a thermosetting resin. The thermosetting resin may be at least one selected from the group consisting of, for example, an epoxy resin, a phenol resin and a polyamide-imide resin. When the resin composition contains both an epoxy resin and a phenol resin, the phenol resin may function as a curing agent for the epoxy resin. The resin composition may include a thermoplastic resin. The thermoplastic resin may be at least one selected from the group consisting of, for example, acrylic resin, polyethylene, polypropylene, polystyrene, polyvinyl chloride, and polyethylene terephthalate. The resin composition may contain both a thermosetting resin and a thermoplastic resin. The resin composition may contain a silicone resin.

The epoxy resin may be, for example, a resin having two or more epoxy groups in one molecule. Epoxy resins include, for example, biphenyl type epoxy resin, stillben type epoxy resin, diphenylmethane type epoxy resin, sulfur atom-containing epoxy resin, novolak type epoxy resin, dicyclopentadiene type epoxy resin, salicylaldehyde type epoxy resin, naphthols and phenol. Copolymerization type epoxy resin, aralkyl type phenol resin epoxie, bisphenol type epoxy resin, alcohols glycidyl ether type epoxy resin, paraxylylene and / or metaxylylene modified phenol resin glycidyl ether type epoxy resin, terpen modified phenol resin Glycidyl ether type epoxy resin, cyclopentadiene type epoxy resin, glycidyl ether type epoxy resin of polycyclic aromatic ring modified phenol resin, glycidyl ether type epoxy resin of naphthalene ring containing phenol resin, glycidyl ester type epoxy resin, glycidyl type or methyl glycidyl Type epoxy resin, alicyclic epoxy resin, halogenated phenol novolac type epoxy resin, orthocresol novolac type epoxy resin, hydroquinone type epoxy resin, trimethylolpropane type epoxy resin, and olefin bonds are oxidized with a peracid such as peracetic acid. It may be at least one selected from the group consisting of the linear aliphatic epoxy resin thus obtained.

Among the epoxy resins, crystalline epoxy resins are preferable. Although the molecular weight of the crystalline epoxy resin is relatively low, the crystalline epoxy resin has a relatively high melting point and is excellent in fluidity. The crystalline epoxy resin (highly crystalline epoxy resin) may be at least one selected from the group consisting of, for example, a hydroquinone type epoxy resin, a bisphenol type epoxy resin, a thioether type epoxy resin, and a biphenyl type epoxy resin. Commercially available crystalline epoxy resins include, for example, Epicron 860, Epicron 1050, Epicron 1055, Epicron 2050, Epicron 3050, Epicron 4050, Epicron 7050, Epicron HM-091, Epicron HM-101, Epicron N-730A, Epicron N. -740, Epicron N-770, Epicron N-775, Epicron N-865, Epicron HP-4032D, Epicron HP-7200L, Epicron HP-7200, Epicron HP-7200H, Epicron HP-7200HH, Epicron HP-7200HH, Epicron HP -4700, Epicron HP-4710, Epicron HP-4770, Epicron HP-5000, Epicron HP-6000, and N500P-2 (above, trade name manufactured by DIC Co., Ltd.), NC-3000, NC-3000-L, NC -3000-H, NC-3100, CER-3000-L, NC-2000-L, XD-1000, NC-7000-L, NC-7300-L, EPPN-501H, EPPN-501HY, EPPN-502H, EOCN -1020, EOCN-102S, EOCN-103S, EOCN-104S, CER-1020, EPPN-201, BREN-S, BREN-10S (above, trade name manufactured by Nippon Kayaku Co., Ltd.), YX-4000, YX- It may be at least one selected from the group consisting of 4000H, YL4121H, and YX-8800 (above, trade name manufactured by Mitsubishi Chemical Co., Ltd.).

The resin composition may contain one of the above epoxy resins. The resin composition may contain a plurality of types of epoxy resins among the above.

The curing agent is classified into a curing agent that cures the resin in the range of low temperature to room temperature and a heat curing type curing agent that cures the resin with heating. Hardeners that cure the resin in the low temperature to room temperature range are, for example, aliphatic polyamines, polyaminoamides, and polymercaptans. The heat-curable curing agent is, for example, aromatic polyamine, acid anhydride, phenol resin, phenol novolac resin, dicyandiamide (DICY) and the like.

The phenolic resin is, for example, an aralkyl type phenol resin, a dicyclopentadiene type phenol resin, a salicylaldehyde type phenol resin, a novolac type phenol resin, a copolymerized phenol resin of benzaldehyde type phenol and an aralkyl type phenol, paraxylylene and / or metaxylylene modification. From the group consisting of phenol resin, melamine-modified phenol resin, terpen-modified phenol resin, dicyclopentadiene-type naphthol resin, cyclopentadiene-modified phenol resin, polycyclic aromatic ring-modified phenol resin, biphenyl-type phenol resin, and triphenylmethane-type phenol resin. It may be at least one of the choices. The phenol resin may be a copolymer composed of two or more of the above. As a commercially available phenol resin, for example, Tamanol 758 manufactured by Arakawa Chemical Industry Co., Ltd., HP-850N manufactured by Hitachi Chemical Co., Ltd., or the like may be used.

The phenol novolac resin may be, for example, a resin obtained by condensing or cocondensing phenols and / or naphthols and aldehydes under an acidic catalyst. The phenols constituting the phenol novolac resin may be at least one selected from the group consisting of, for example, phenol, cresol, xylenol, resorcin, catechol, bisphenol A, bisphenol F, phenylphenol and aminophenol. The naphthols constituting the phenol novolac resin may be at least one selected from the group consisting of, for example, α-naphthol, β-naphthol and dihydroxynaphthalene. The aldehydes constituting the phenol novolac resin may be at least one selected from the group consisting of, for example, formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde and salicylaldehyde.

The curing agent may be, for example, a compound having two phenolic hydroxyl groups in one molecule. The compound having two phenolic hydroxyl groups in one molecule may be at least one selected from the group consisting of, for example, resorcin, catechol, bisphenol A, bisphenol F, and substituted or unsubstituted biphenol.

The resin composition may contain one of the above phenolic resins. The resin composition may include a plurality of types of phenol resins among the above. The resin composition may contain one of the above curing agents. The resin composition may contain a plurality of types of curing agents among the above. As a commercially available phenol resin, for example, Tamanol 758 manufactured by Arakawa Chemical Industry Co., Ltd., HP-850N manufactured by Hitachi Chemical Co., Ltd., or the like may be used.

The ratio of active groups (phenolic OH groups) in the curing agent that reacts with the epoxy groups in the epoxy resin is preferably 0.5 to 1.5 equivalents, more preferably 0.5 equivalents, relative to 1 equivalent of the epoxy groups in the epoxy resin. May be 0.9 to 1.4 equivalents, more preferably 1.0 to 1.2 equivalents. When the ratio of active groups in the curing agent is less than 0.5 equivalent, the amount of OH per unit weight of the cured epoxy resin is reduced, and the curing rate of the resin composition (epoxy resin) is reduced. If the ratio of active groups in the curing agent is less than 0.5 equivalent, the glass transition temperature of the obtained cured product may be low, or a sufficient elastic modulus of the cured product may not be obtained. On the other hand, when the ratio of active groups in the curing agent exceeds 1.5 equivalents, the mechanical strength of the encapsulant formed from the compound tends to decrease. However, even when the ratio of active groups in the curing agent is out of the above range, the effect according to the present invention can be obtained.

The curing accelerator is not limited as long as it is a composition that reacts with the epoxy resin to accelerate the curing of the epoxy resin. The curing accelerator may be, for example, an alkyl group-substituted imidazole or an imidazole such as benzimidazole. The resin composition may include a kind of curing accelerator. The resin composition may include a plurality of types of curing accelerators. When the resin composition contains a curing accelerator, the moldability and releasability of the compound are likely to be improved. When the resin composition contains a curing accelerator, the mechanical strength of the encapsulant produced by using the compound is improved, and the storage stability of the compound in a high temperature and high humidity environment is improved. .. Commercially available imidazole-based curing accelerators include, for example, 2MZ-H, C11Z, C17Z, 1,2DMZ, 2E4MZ, 2PZ-PW, 2P4MZ, 1B2MZ, 1B2PZ, 2MZ-CN, C11Z-CN, 2E4MZ-CN, 2PZ. -At least one selected from the group consisting of CN, C11Z-CNS, 2P4MHZ, TPZ, and SFZ (above, trade name manufactured by Shikoku Chemicals Corporation) may be used. Among these, an imidazole-based curing accelerator having a long-chain alkyl group is preferable, and C11Z-CN (1-cyanoethyl-2-undecylimidazole) is preferable.

The amount of the curing accelerator to be blended is not particularly limited as long as it can obtain the curing promoting effect. However, from the viewpoint of improving the curability and fluidity of the resin composition during moisture absorption, the amount of the curing accelerator is preferably 0.1 to 30 parts by mass, based on 100 parts by mass of the epoxy resin. It may be preferably 1 to 15 parts by mass. The content of the curing accelerator is preferably 0.001 part by mass or more and 5 parts by mass or less with respect to the total mass of the epoxy resin and the curing agent (for example, phenol resin). When the blending amount of the curing accelerator is less than 0.1 parts by mass, it is difficult to obtain a sufficient curing promoting effect. When the blending amount of the curing accelerator exceeds 30 parts by mass, the storage stability of the compound tends to decrease. However, even when the blending amount and content of the curing accelerator are out of the above range, the effect according to the present invention can be obtained.

The coupling agent improves the adhesion between the resin composition and the metal filler, and improves the flexibility and mechanical strength of the encapsulant formed from the compound. The coupling agent may be, for example, at least one selected from the group consisting of a silane compound (silane coupling agent), a titanium compound, an aluminum compound (aluminum chelate), and an aluminum / zirconium compound. The silane coupling agent may be at least one selected from the group consisting of, for example, epoxysilane, mercaptosilane, aminosilane, alkylsilane, ureidosilane, acid anhydride-based silane, and vinylsilane. In particular, an aminophenyl-based silane coupling agent is preferable. The compound may include one of the above coupling agents, and may include a plurality of the above coupling agents.

Due to the environmental safety, recyclability, molding processability and low cost of the compound, the compound may contain a flame retardant. The flame retardant is at least one selected from the group consisting of, for example, a brominated flame retardant, a scale flame retardant, a hydrated metal compound flame retardant, a silicone flame retardant, a nitrogen-containing compound, a hindered amine compound, an organic metal compound and an aromatic empra. It may be. The compound may be provided with one of the above flame retardants, and may be provided with a plurality of the above flame retardants.

The resin composition may contain wax. The wax enhances the fluidity of the compound in the molding of the compound (for example, transfer molding) and functions as a mold release agent. The wax may be at least one of fatty acids such as higher fatty acids and fatty acid esters.

The wax is, for example, fatty acids such as montanic acid, stearic acid, 12-oxystearic acid, laurate or esters thereof; zinc stearate, calcium stearate, barium steaenoate, aluminum stearate, magnesium stearate, calcium laurate, Fatty acid salts such as zinc linoleate, calcium ricinolate, zinc 2-ethylhexoneate; stearic acid amide, oleic acid amide, erucic acid amide, bechenic acid amide, palmitate amide, laurate amide, hydroxystearic acid amide, methylene bisstearate. Acid amide, ethylene bisstearic acid amide, ethylene bislauric acid amide, distearyl adipate amide, ethylene bisoleic acid amide, diorail adipic acid amide, N-stearyl stearic acid amide, N-oleyl stearic acid amide, N-stearyl Fatty acid amides such as erucate amide, methylol stearic acid amide, methylol bechenic acid amide; fatty acid esters such as butyl stearate; alcohols such as ethylene glycol and stearyl alcohol; polyethylene glycol, polypropylene glycol, polytetramethylene glycol and modifications thereof. Polyethers made of materials; Polysiloxanes such as silicone oil and silicon grease; Fluorine compounds such as fluorine oil, fluorine grease, and fluorine-containing resin powder; and paraffin wax, polyethylene wax, amide wax, polypropylene wax, and esters It may be at least one selected from the group consisting of waxes such as wax, carnauba, and microwax;

The compound according to this embodiment has excellent fluidity. Therefore, the compound according to the present embodiment can be easily processed into a desired shape by extrusion molding or transfer molding (transfer molding). Based on the composition of the metal filler or the resin composition, various physical properties of the molded product containing the compound or the cured product of the compound can be freely controlled. The physical properties are, for example, electromagnetic properties or thermal conductivity. For these reasons, the compound can be used in various industrial products or their raw materials. Industrial products manufactured using the compound may be, for example, automobiles, medical devices, electronic devices, electrical devices, information and communication devices, home appliances, audio devices, and general industrial devices. When the compound contains a soft magnetic material as a metal filler, the compound may be used as a sealing material for an inductor, a magnetic core for an inductor, an EMI shield, or a magnetic core for a transformer. If the compound contains a metal magnet as a metal filler, the compound may be used as a raw material for the bonded magnet.

(Manufacturing method of compound)
In the following, an example of a method for producing a compound according to the present invention will be described. However, the method for producing a compound according to the present invention is not limited to the following production method.

The compound manufacturing method according to the present embodiment includes a first mixing step, a second mixing step, a cooling step, and a crushing step.

In the first mixing step, the first mixture is obtained by mixing the metal filler and the clotting agent. By the first mixing step, the coupling agent is bonded to the surface of each metal particle constituting the metal filler. That is, a part or the whole of the surface of each metal particle is covered with the coupling agent. As a result, the surface of the metal filler is easily covered with the resin composition via the coupling agent, the metal filler is easily dispersed in the compound, and the filling rate of the metal filler in the compound is likely to increase.

The metal filler mixed with the culling agent contains at least the first metal powder. The surface of each primary metal particle contained in the primary metal powder is pre-covered with Si-containing glass. Since the filling rate of the metal filler in the compound tends to increase, the metal filler mixed with the culling agent preferably contains both the first metal powder and the second metal powder. The surface of each secondary metal particle contained in the secondary metal powder does not have to be covered with glass containing Si. The surface of each secondary metal particle contained in the secondary metal powder may be pre-covered with glass containing Si. When the metal filler contains both the first metal powder and the second metal powder, the metal filler may be obtained by mixing the first metal powder and the second metal powder before the first mixing step.

In the second mixing step following the first mixing step, the second mixture is obtained by kneading the resin composition excluding the curling agent and the first mixture while heating. That is, in the second mixing step, the first mixture is kneaded with the components of the resin composition other than the coupling agent. The components of the resin composition other than the coupling agent may be, for example, a thermosetting resin, a curing agent, a curing accelerator, and an additive. The additive may be, for example, at least one of a wax and a flame retardant. A resin mixture may be obtained by premixing the thermosetting tree resin, the curing agent, the curing accelerator and the additive before the second mixing step. Then, in the second mixing step, the second mixture may be obtained by kneading the resin mixture and the first mixture while heating. The second mixture may be a paste.

The temperature of the second mixture in the second mixing step may be adjusted according to the composition of the resin composition. The temperature of the second mixture in the second mixing step may be, for example, 50 ° C. or higher and 150 ° C. or lower, preferably 60 ° C. or higher and 120 ° C. or lower, more preferably 80 ° C. or higher and 110 ° C. or lower. When the temperature of the second mixture is within the above range, the resin composition in the second mixture is likely to soften, the resin composition is likely to cover the surface of the metal particles, and the resin composition in the second mixing step is likely to be softened. Hardening is easily suppressed. If the temperature of the second mixture is too low, the second mixture will not be sufficiently kneaded, the moldability of the compound will be impaired, and the degree of curing of the compound will vary. If the temperature of the second mixture is too high, the resin composition will be cured during the second mixing step, and the fluidity and moldability of the compound will be easily impaired. The time for kneading the second mixture in the second mixing step may be adjusted according to the performance of the kneading means (for example, a biaxial pressure kneader) used in the second mixing step and the volume of the second mixture.

In the cooling step following the second mixing step, a solid substance can be obtained by cooling the second mixture. The second mixture may be cooled at room temperature.

In the crushing process following the cooling process, the solid matter is crushed. The powder itself obtained by pulverizing the solid material may be used as a compound. Coarse particles may be removed from the powder by classification of the powder obtained by the grinding step. A tablet made of a compound may be produced by molding the powder obtained by the pulverization step.

The compound is completed by the above manufacturing method.

The present invention will be described in more detail by the following examples and comparative examples. However, the present invention is not limited to the following examples.

(Example 1)
[Making compound powder]
<Preparation of metal filler>
The first metal powder and the second metal powder were put in a bag, and the bag was closed. A metal filler was obtained by shaking the bag with both hands for 3 minutes to mix the first metal powder and the second metal powder. The bag was made of PE (polyethylene). The size of the bag was 470 mm x 670 mm.

The first metal powder was composed of a large number of first metal particles. The median diameter of the first metal powder was 2.17 μm or more and 2.31 μm or less. Each first metal particle was composed of an alloy particle and a large number of glass particles covering the surface of the alloy particle. Each alloy particle contained Fe, Cr and Si. Each glass particle covering the surface of the alloy particles contained Si. The particle size of each glass particle was significantly smaller than the median diameter of the first metal powder. Each first metal particle was substantially spherical. The mass M1 of the first metal powder was 770.8 g.

As the second metal powder, an amorphous alloy powder containing iron was used. The powder of the amorphous alloy containing iron was KUAMET 9A4-II manufactured by Epson Atmix Co., Ltd. The median diameter of the second metal powder was 25.0 μm. The amorphous alloy particles (second metal particles) constituting the second metal powder were substantially spherical. The mass M2 of the second metal powder was 351.1.2 g.

100 × M1 / (M1 + M2) was 18. 100 × M2 / (M1 + M2) was 82.

<First mixing process>
Methacrylic silane (silane coupling agent) was added to the metal filler in the bag. The mass of methacrylic silane was 5.43 g. The methacrylic silane was KBM-503 manufactured by Shin-Etsu Chemical Co., Ltd. The first mixture was obtained by shaking the bag with both hands for 3 minutes to mix the metal filler and methacrylic silane. By the first mixing step, the surface of each metal particle constituting the metal filler was covered with methacrylic silane.

<Second mixing process>
In the second mixing step, a bag different from the above bag was used. The size of the bag used in the second mixing step was 205 × 300 mm. This bag was made of PE (polyethylene). A thermosetting resin, a curing agent, a curing accelerator and a wax powder were put in a bag, and the bag was closed. The resin mixture was obtained by shaking the bag with both hands for 3 minutes to mix the contents of the bag. The masses and compositions of the thermosetting resin, the curing agent, the curing accelerator, and the wax powder are shown below. Both NC3000-H and NC3000 below are epoxy resins.
90.9 g of thermosetting resin (NC3000-H manufactured by Nippon Kayaku Co., Ltd.)
39.0 g of thermosetting resin (NC3000 manufactured by Nippon Kayaku Co., Ltd.)
48.2 g of curing agent (phenol novolac resin, HP-850N manufactured by Hitachi Chemical Co., Ltd.)
2.6 g of curing accelerator (imidazole epoxy resin curing agent, C17Z manufactured by Shikoku Chemicals Corporation)
15.7g of wax powder (Licowax E manufactured by Clariant Chemicals Co., Ltd.)

The above first mixture and resin mixture were placed in a tank of a biaxial pressure kneader. The first mixture and the resin mixture in the tank were kneaded while being pressurized with a kneader to obtain a second mixture. The second mixture was a paste. The temperature in the tank during kneading was 82 ° C. The rotation speed of the kneader was 40 rpm. The kneading time was 1 minute. As the biaxial pressure kneader, a pressure kneader (PS1-5MHB-H type kneader) manufactured by Nihon Spindle Manufacturing Co., Ltd. (formerly Moriyama Seisakusho Co., Ltd.) was used.

<Cooling process>
The second mixture was cooled at room temperature to give a solid.

<Crushing process>
The solid material was pulverized to obtain a powdery compound. Coarse particles were removed from the compound due to sieving. The mesh size of the sieve was 2 mm.

The compound of Example 1 was prepared by the above method. The content (space factor) of the metal filler in the compound was 95.5% by mass.

[Evaluation of liquidity]
The compound of Example 1 was charged into a transfer tester. The amount of spiral flow of the compound was measured at a mold temperature of 175 ° C., an injection pressure of 4.1 MPa, and a molding time of 420 seconds. The amount of spiral flow is the length at which the compound flows in the groove formed in the mold. That is, the spiral flow amount is the flow distance of the softened or liquefied compound. The shape of the groove through which the compound flows is a spiral curve (Archimedes spiral). The easier the compound flows, the greater the amount of spiral flow. That is, the amount of spiral flow of the compound having excellent fluidity is large. As the transfer tester, a 100KN transfer molding machine (PZ-10 type) manufactured by Kodaira Seisakusho Co., Ltd. was used. As the mold, a mold for measuring spiral flow according to ASTM D3123 was used. The amount of spiral flow of Example 1 is shown in Table 1 below.

[Measurement of relative magnetic permeability]
Using a transfer tester and a mold, a toroidal molded body was produced from the compound of Example 1. The mold temperature was 175 ° C., the injection pressure was 4.1 MPa, and the molding time was 420 seconds. The dimensions of the molded body were an outer diameter of 20 mm, an inner diameter of 12 mm, and a thickness of 2 mm. As the transfer tester, a 100KN transfer molding machine (PZ-10 type) manufactured by Kodaira Seisakusho Co., Ltd. was used. As the mold, a mold capable of obtaining a toroidal shape was used. The primary winding was wound around the molded body for 5 turns, and the secondary winding was wound around the molded body for 5 turns. The relative magnetic permeability μ _S of the sample prepared by the above method was measured. The relative magnetic permeability μ _S of Example 1 is shown in Table 1 below. A BH analyzer (SY-8258) manufactured by Iwatsu Electric Co., Ltd. was used for the measurement of the relative magnetic permeability μ _S. The frequency at the time of measuring the relative permeability was 1 MHz.

(Example 2)
By changing the mass ratio of the first mixture and the resin mixture, the content of the metal filler in the compound of Example 2 was adjusted to 95.0% by mass. The compound of Example 2 was prepared in the same manner as in Example 1 except for the content of the metal filler. The amount of spiral flow of the compound of Example 2 was measured by the same method as in Example 1. The amount of spiral flow of Example 2 is shown in Table 1 below. The relative magnetic permeability of the compound of Example 2 was measured by the same method as in Example 1. The relative magnetic permeability of Example 2 is shown in Table 1 below.

(Comparative Example 1)
Only the second metal powder was used as the metal filler of Comparative Example 1. Similar to Example 1, the content of the metal filler in the compound of Comparative Example 1 was adjusted to 95.5% by mass. The compound of Comparative Example 1 was prepared in the same manner as in Example 1 except that the metal filler was removed. The spiral flow amount of the compound of Comparative Example 1 was measured by the same method as in Example 1. The amount of spiral flow of Comparative Example 1 is shown in Table 1 below. The relative magnetic permeability of the compound of Comparative Example 1 was measured by the same method as in Example 1. The relative magnetic permeability of Comparative Example 1 is shown in Table 1 below.

(Comparative Example 2)
Only the second metal powder was used as the metal filler of Comparative Example 2. Similar to Example 2, the content of the metal filler in the compound of Comparative Example 2 was adjusted to 95.0% by mass. The compound of Comparative Example 2 was prepared in the same manner as in Example 1 except for the metal filler and its content. The spiral flow amount of the compound of Comparative Example 2 was measured by the same method as in Example 1. The amount of spiral flow in Comparative Example 2 is shown in Table 1 below. The relative magnetic permeability of the compound of Comparative Example 2 was measured by the same method as in Example 1. The relative magnetic permeability of Comparative Example 2 is shown in Table 1 below.

Since the compound according to the present invention has excellent fluidity, it is easy to be molded according to the shape of various industrial products.

Claims

The metal filler containing the first metal powder and the resin composition are provided.
The first metal powder contains a plurality of first metal particles and contains a plurality of first metal particles.
At least a part of the surface of the first metal particles is covered with glass containing Si.
The median diameter of the first metal powder is 1.0 μm or more and 5.0 μm or less.
compound.
The first metal powder is an alloy containing Fe.
The compound according to claim 1.
The first metal particles are spherical,
The compound according to claim 1 or 2.
The resin composition contains a thermosetting resin.
The compound according to any one of claims 1 to 3.
Powder or paste,
The compound according to any one of claims 1 to 4.
The content of the metal filler is 90% by mass or more and less than 100% by mass.
The compound according to any one of claims 1 to 5.
The metal filler further comprises a second metal powder
The median diameter of the second metal powder is larger than the median diameter of the first metal powder.
The compound according to any one of claims 1 to 6.
The median diameter of the second metal powder is 20.0 μm or more and 30.0 μm or less.
The mass of the first metal powder is M1.
The mass of the second metal powder is M2,
100 × M1 / (M1 + M2) is 5 or more and 30 or less.
100 × M2 / (M1 + M2) is 70 or more and 95 or less.
The compound according to claim 7.
The second metal powder is an alloy containing Fe.
The compound according to claim 7 or 8.
The second metal particles contained in the second metal powder are spherical.
The compound according to any one of claims 7 to 9.
The D90 of the second metal powder is 40 μm or more and 65 μm or less.
The compound according to any one of claims 7 to 10.
Including the compound according to any one of claims 1 to 11.
Molded body.
The cured product of the compound according to any one of claims 1 to 11.
The method for producing the compound according to any one of claims 1 to 6.
The step of obtaining the first mixture by mixing the metal filler and the clotting agent, and
A step of obtaining a second mixture by kneading the resin composition excluding the clotting agent and the first mixture while heating.
A step of obtaining a solid substance by cooling the second mixture, and
The step of crushing the solid matter and
To prepare
How to make the compound.
The method for producing the compound according to any one of claims 7 to 11.
The step of obtaining the metal filler by mixing the first metal powder and the second metal powder, and
The step of obtaining the first mixture by mixing the metal filler and the clotting agent, and
A step of obtaining a second mixture by kneading the resin composition excluding the clotting agent and the first mixture while heating.
A step of obtaining a solid substance by cooling the second mixture, and
The step of crushing the solid matter and
To prepare
How to make the compound.