Composite and shaped body

Abstract

A composite having a powder containing a metal element and a resin composition, the resin composition containing an epoxy resin and a compound having a siloxane bond, the content of the compound having a siloxane bond being 20 parts by mass or less relative to 100 parts by mass of the epoxy resin, the compound having a siloxane bond including a siloxane compound having a structure represented by the following formula (1).

Description

TECHNICAL FIELD

[0001] The present application relates to a composite and a molded body. BACKGROUND

[0002] A composite containing a metal powder and a resin composition is used as a raw material for various industrial products such as an inductor, an electromagnetic shield, or a bonded magnet, for example, depending on various physical properties of the metal powder (see Patent Document 1 below).

[0003] PRIOR ART DOCUMENTS

[0004] PATENT DOCUMENT

[0005] Patent Document 1: Japanese Patent Application Publication No. 2014-13803 SUMMARY

[0006] PROBLEMS TO BE SOLVED BY THE INVENTION

[0007] Sometimes, an industrial product such as an inductor is required to have resistance to heat or voltage. An object of the present application is to provide a composite capable of obtaining a molded body having both heat resistance and voltage resistance, and a molded body having the composite.

[0008] MEANS FOR SOLVING THE PROBLEMS

[0009] The composite of one aspect of the present application has a powder containing a metal element and a resin composition, the resin composition containing an epoxy resin and a chemical compound having a siloxane bond, the content of the chemical compound having a siloxane bond being 20 parts by mass or less with respect to 100 parts by mass of the epoxy resin, and the chemical compound having a siloxane bond containing a siloxane compound having a structure represented by the following Chemical Formula (1).

[0010]

[0011] In the Chemical Formula (1), n is an integer of 2 to 200, and R 1 and R 2 each independently is an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a monovalent organic group having an epoxy group, a monovalent organic group having a carboxyl group, or a polyalkylene ether group having 3 to 500 carbon atoms.

[0012] In the above composite of one aspect of the present application, the siloxane compound can further have a structural unit represented by the following Chemical Formula (2).

[0013]

[0014] In the formula (2), R 3 is an alkylene group having 1 to 10 carbon atoms.

[0015] The above-mentioned composite of one aspect of the present application can contain a compound represented by the following formula (3) as a siloxane compound.

[0016]

[0017] In the formula (3), n is an integer of 2 to 200, m1 and m2 are each independently an integer of 1 to 200, R 4 , R 5 , R 6 , and R 7 are each independently an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a monovalent organic group having an epoxy group, a monovalent organic group having a carboxyl group, or a polyalkylene ether group having 3 to 500 carbon atoms, R 8 , and R 9 are each independently an alkylene group having 1 to 10 carbon atoms, R 10 , and R 11 are each independently a divalent hydrocarbon group having 1 to 10 carbon atoms which can contain an ether structure.

[0018] The above-mentioned composite of one aspect of the present application can contain at least one of a biphenylene aralkyl type epoxy resin and an isocyanate-modified epoxy resin as an epoxy resin.

[0019] In the above-mentioned composite of one aspect of the present application, the content of the powder containing a metal element can be 90 mass% or more and less than 100 mass%.

[0020] A molded body of one aspect of the present application is provided with the above-mentioned composite.

[0021] Effects of the Invention

[0022] According to the present application, a composite capable of obtaining a molded body having both heat resistance and voltage resistance and a molded body provided with the composite are provided. DETAILED DESCRIPTION

[0023] Hereinafter, a preferred embodiment of the present application will be described. However, the present application is not limited by the following embodiment at all.

[0024] <Summary of Composite>

[0025] The composite of the present embodiment has a powder containing a metal element and a resin composition. The powder containing a metal element is composed of a plurality of (a majority of) particles containing a metal element. The powder containing a metal element (the particle containing a metal element) may, for example, contain at least one selected from the group consisting of a metal monomer, an alloy, and a metal compound. The resin composition contains at least an epoxy resin and a compound having a siloxane bond. The compound having a siloxane bond is sometimes referred to as a "siloxane compound". The resin composition can contain other components in addition to the epoxy resin and the siloxane compound. For example, the resin composition can contain a curing agent. The resin composition can also contain a curing accelerator. The resin composition can also contain an additive. The resin composition can be a component that can include the epoxy resin, the siloxane compound, the curing agent, the curing accelerator, and the additive, and a remaining component (a non-volatile component) other than the organic solvent and the powder containing a metal element. The additive is a component of a remaining portion of the resin composition other than the resin, the siloxane compound, the curing agent, and the curing accelerator. The additive is, for example, a coupling agent or a flame retardant, or the like. The resin composition can contain a wax as an additive. The composite can be a powder (a composite powder).

[0026] The composite of the present embodiment contains a siloxane compound as one of the elastomers in a prescribed amount. The reason why the heat resistance and the voltage resistance of the molded body obtained from the composite by the prescribed amount of the siloxane compound are improved is not clear, but the inventors and the like speculate the following possibilities. First, it is considered that, by adding the siloxane compound, the flowability of the components is improved, and the generation of internal voids at the time of molding can be suppressed. Second, it is considered that, since the powder containing a metal element has low compatibility with the epoxy resin, the properties start to deteriorate from the interface between the two, but by adding the siloxane compound, the compatibility of the two can be improved. However, the effects of the present application are not limited to the above.

[0027] The composite can have a powder containing a metal element and a resin composition attached to the surface of each particle containing a metal element that constitutes the powder containing a metal element. The resin composition can cover the entire surface of the particle, or can cover only a part of the surface of the particle. The composite can also have an uncured resin composition and a powder containing a metal element. The composite can also have a semi-cured product of the resin composition (for example, a B-stage resin composition) and a powder containing a metal element. The composite can also have both an uncured resin composition and a semi-cured product of the resin composition. The composite can also be composed of a powder containing a metal element and a resin composition.

[0028] The content of the metal element-containing powder in the composite can be 90 mass% or more and less than 100 mass%, 90 mass% or more and 99.8 mass% or less, 92 mass% or more and 99.5 mass% or less, 94 mass% or more and 98.5 mass% or less, or 94 mass% or more and 97.5 mass% or less, relative to the mass of the entire composite. The composite can contain other filler materials (for example, a filler of silicon dioxide) in addition to the metal element-containing powder.

[0029] The content of the resin composition in the composite can be 0.2 mass% or more and 10 mass% or less or 4 mass% or more and 6 mass% or less, relative to the mass of the entire composite (for example, the total of the mass of the metal element-containing powder and the mass of the resin composition).

[0030] The content of the siloxane compound in the composite is 20 mass parts or less, relative to 100 mass parts of the epoxy resin, but can also be 17.5 mass parts or less or 15 mass parts or less. When the content of the siloxane compound is within the above range, both heat resistance and voltage resistance of the molded body can be taken into account. On the other hand, the lower limit of the content of the siloxane compound in the composite is not particularly limited, but from the viewpoint of moldability and the like, it can be 0.1 mass parts or more, 5 mass parts or more, 7.5 mass parts or more, or 10 mass parts or more, relative to 100 mass parts of the epoxy resin.

[0031] The average particle diameter of the metal element-containing powder is not particularly limited and can be, for example, 1 μm or more and 300 μm or less. The average particle diameter can be measured, for example, by a particle size distribution meter. The shape of each metal element-containing particle constituting the metal element-containing powder is not limited and can be, for example, spherical, flat, angular columnar, or needle-like. The composite can have a plurality of metal element-containing powders having different average particle diameters.

[0032] According to the composition or combination of the metal element-containing powder included in the composite, the electromagnetic properties and the like of the shaped body formed from the composite are freely controlled, and the shaped body can be used as various industrial products or raw materials for these. The industrial products manufactured using the composite can be, for example, automobiles, medical equipment, electronic equipment, electrical equipment, information communication equipment, home electric appliances, audio equipment, and general industrial equipment. For example, when the composite includes a permanent magnet such as a Sm-Fe-N-based alloy or a Nd-Fe-B-based alloy as the metal element-containing powder, the composite can be used as a raw material for a bonded magnet. When the composite includes a soft magnetic powder such as a Fe-Si-Cr-based alloy or a ferrite as the metal element-containing powder, the composite can be used as a raw material (for example, a magnetic core) for an inductor (for example, an EMI filter) or a transformer. When the composite includes iron and copper as the metal element-containing powder, the shaped body (for example, a sheet) formed from the composite can be used as an electromagnetic wave shield.

[0033] <Composition of the composite>

[0034] <Resin composition>

[0035] The resin composition has a function as a binding material (binder) of the metal element-containing particles constituting the metal element-containing powder, and imparts mechanical strength to the shaped body formed from the composite. For example, when the composite is formed at high pressure using a mold, the resin composition is filled between the metal element-containing particles, and the metal element-containing particles are bonded to each other. By curing the resin composition in the shaped body, the cured product of the resin composition causes the metal element-containing particles to be more firmly bonded to each other, and the mechanical strength of the shaped body is improved.

[0036] The resin composition contains at least an epoxy resin as a thermosetting resin. By the composite including an epoxy resin having superior fluidity among thermosetting resins, the fluidity, storage stability, and formability of the composite are improved. However, the composite can include other resins in addition to the epoxy resin, as long as the effects of the present application are not impaired. For example, the resin composition can include at least one of a phenol resin and a polyamide-imide resin as a thermosetting resin. When the resin composition includes both an epoxy resin and a phenol resin, the phenol resin can function as a curing agent for the epoxy resin. The resin composition can also include a thermoplastic resin. The thermoplastic resin can be, for example, at least one selected from the group consisting of an acrylic resin, polyethylene, polypropylene, polystyrene, polyvinyl chloride, and polyethylene terephthalate. The resin composition can include both a thermosetting resin and a thermoplastic resin. The resin composition can also include a silicone resin.

[0037] The epoxy resin may, for example, be a resin having two or more epoxy groups in one molecule. The epoxy resin may, for example, also be a resin having three or more epoxy groups in one molecule. The epoxy resin may also be a multifunctional epoxy resin. The epoxy resin may, for example, be at least one selected from the group consisting of a biphenyl-type epoxy resin, a stilbene-type epoxy resin, a diphenylmethane-type epoxy resin, a sulfur atom-containing epoxy resin, a novolak-type epoxy resin, a dicyclopentadiene-type epoxy resin, a salicylaldehyde-type epoxy resin, a copolymer-type epoxy resin of naphthol and phenol, an epoxide of an aralkyl-type phenol aldehyde resin, a bisphenol-type epoxy resin, an epoxy resin containing a bisphenol skeleton, an epoxy propyl ether-type epoxy resin of an alcohol, an epoxy propyl ether-type epoxy resin of a p- and / or m-xylene modified phenol aldehyde resin, an epoxy propyl ether-type epoxy resin of a terpene modified phenol aldehyde resin, a cyclopentadiene-type epoxy resin, an epoxy propyl ether-type epoxy resin of a polycyclic aromatic ring modified phenol aldehyde resin, an epoxy propyl ether-type epoxy resin of a naphthalene ring-containing phenol aldehyde resin, an epoxy propyl ester-type epoxy resin, an epoxy propyl-type or a methyl epoxy propyl-type epoxy resin, an alicyclic-type epoxy resin, a halogenated phenol novolak-type epoxy resin, an o-cresol novolak-type epoxy resin, a p-phenol-type epoxy resin, a trimethylolpropane-type epoxy resin, and a linear aliphatic epoxy resin obtained by oxidizing an olefinic bond with a peroxo acid such as peroxo acetic acid.

[0038] From the viewpoint of excellent fluidity, the epoxy resin may be at least one selected from the group consisting of a biphenyl-type epoxy resin, an o-cresol novolak-type epoxy resin, a phenol novolak-type epoxy resin, a bisphenol-type epoxy resin, an epoxy resin having a bisphenol skeleton, a salicylaldehyde novolak-type epoxy resin, and a naphthol novolak-type epoxy resin.

[0039] The epoxy resin can be a crystalline epoxy resin. Although the molecular weight of the crystalline epoxy resin is relatively low, the crystalline epoxy resin has a relatively high melting point and excellent flowability. The crystalline epoxy resin (highly crystalline epoxy resin) can be, for example, at least one selected from the group consisting of a hydroquinone type epoxy resin, a bisphenol type epoxy resin, a thioether type epoxy resin, and a biphenyl type epoxy resin. Commercially available products of the crystalline epoxy resin can be, for example, at least one selected from the group consisting of EPICLON 860, EPICLON 1050, EPICLON 1055, EPICLON 2050, EPICLON 3050, EPICLON 4050, EPICLON 7050, EPICLON HM-091, EPICLON HM-101, EPICLON N-730A, EPICLON N-740, EPICLON N-770, EPICLON N-775, EPICLON N-865, EPICLON HP-4032D, EPICLON HP-7200L, EPICLON HP-7200, EPICLON HP-7200H, EPICLON HP-7200HH, EPICLON HP-7200HHH, EPICLON HP-4700, EPICLON HP-4710, EPICLON HP-4770, EPICLON HP-5000, EPICLON HP-6000, N500P-2, and N500P-10 (all are trade names of DIC Corporation), 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 (all are trade names of Nippon Kayaku Co., Ltd.), YX-4000, YX-4000H, YL4121H, and YX-8800 (all are trade names of Mitsubishi Chemical Corporation).

[0040] The resin composition can contain at least one of a biphenylene aralkyl type epoxy resin and an isocyanate-modified epoxy resin as the epoxy resin from the viewpoint that the molding shrinkage from the molding of the composite is easily reduced and the heat resistance and voltage resistance of the molded body are easily improved. The resin composition can also contain both of a biphenylene aralkyl type epoxy resin and an isocyanate-modified epoxy resin as the epoxy resin. A commercially available product of the biphenylene aralkyl type epoxy resin can be, for example, NC-3000 manufactured by Nippon Kayaku Co., Ltd. A commercially available product of the isocyanate-modified epoxy resin can be, for example, AER-4001 manufactured by Asahi Kasei Corporation (former Asahi Kasei E-Materials Co., Ltd.). The resin composition can contain a multifunctional epoxy resin from the viewpoint that the heat resistance and voltage resistance of the molded body are easily improved. A commercially available product of the multifunctional epoxy resin can be, for example, VG-3101L manufactured by Printec Corporation, and the like.

[0041] The resin composition can contain one of the above-described epoxy resins. The resin composition can also contain a plurality of the above-described epoxy resins.

[0042] Curing agents are classified into a curing agent that cures an epoxy resin in a range from low temperature to room temperature and a heat-curing type curing agent that cures an epoxy resin with heating. The curing agent that cures an epoxy resin in a range from low temperature to room temperature is, for example, an aliphatic polyamine, a polyaminoamide, a polythiol, and the like. The heat-curing type curing agent is, for example, an aromatic polyamine, an acid anhydride, a phenol novolak resin, dicyandiamide (DICY), and the like.

[0043] When a curing agent that cures an epoxy resin in a range from low temperature to room temperature is used, the glass transition point of the cured product of the epoxy resin tends to be low and the cured product of the epoxy resin is soft. As a result, the molded body formed from the composite also tends to be soft. On the other hand, from the viewpoint of improving the heat resistance of the molded body, the curing agent can be preferably a heat-curing type curing agent, more preferably a phenol resin, and further preferably a phenol novolak resin. In particular, by using a phenol novolak resin as the curing agent, the cured product of the epoxy resin with a high glass transition point is easily obtained. As a result, the heat resistance and mechanical strength of the molded body are easily improved.

[0044] The phenol formaldehyde resin may, for example, be at least one selected from the group consisting of aralkyl type phenol formaldehyde resin, dicyclopentadiene type phenol formaldehyde resin, salicylaldehyde type phenol formaldehyde resin, novolak type phenol formaldehyde resin, copolymer type phenol formaldehyde resin of benzaldehyde type phenol and aralkyl type phenol, p-xylene and / or m-xylene modified phenol formaldehyde resin, melamine modified phenol formaldehyde resin, terpene modified phenol formaldehyde resin, dicyclopentadiene type naphthol formaldehyde resin, cyclopentadiene modified phenol formaldehyde resin, polycyclic aromatic ring modified phenol formaldehyde resin, biphenyl type phenol formaldehyde resin, and triphenylmethane type phenol formaldehyde resin. The phenol formaldehyde resin can also be a copolymer composed of two or more of the above. As a commercially available product of the phenol formaldehyde resin, for example, Tamanol 758 manufactured by Arakawa Chemical Industries, Ltd., HP-850N manufactured by Hitachi Chemical Co., Ltd., and the like can be used.

[0045] The phenol novolak resin may, for example, be a resin obtained by condensation or co-condensation of a phenol and / or naphthol with an aldehyde under an acidic catalyst. The phenol constituting the phenol novolak resin may, for example, be at least one selected from the group consisting of phenol, cresol, xylenol, resorcinol, catechol, bisphenol A, bisphenol F, phenylphenol, and aminophenol. The naphthol constituting the phenol novolak resin may, for example, be at least one selected from the group consisting of a-naphthol, β-naphthol, and dihydroxynaphthalene. The aldehyde constituting the phenol novolak resin may, for example, be at least one selected from the group consisting of formaldehyde, acetaldehyde, propylaldehyde, benzaldehyde, and salicylaldehyde. As a commercially available product of the phenol novolak resin, for example, HF-3M manufactured by Meiwa Plastic Industries, Ltd., MEW-1800, and the like can be mentioned.

[0046] The curing agent may, for example, also be a compound having two phenolic hydroxyl groups in one molecule. The compound having two phenolic hydroxyl groups in one molecule may, for example, be at least one selected from the group consisting of resorcinol, catechol, bisphenol A, bisphenol F, and substituted or unsubstituted diphenylolpropane.

[0047] The resin composition can contain one of the above-mentioned phenol formaldehyde resins. The resin composition can also have a plurality of the above-mentioned phenol formaldehyde resins. The resin composition can contain one of the above-mentioned curing agents. The resin composition can also contain a plurality of the above-mentioned curing agents.

[0048] The ratio of the active group (phenolic OH group) in the curing agent that reacts with the epoxy group in the epoxy resin, relative to 1 equivalent of the epoxy group in the epoxy resin, can preferably be 0.5 to 1.5 equivalents, more preferably 0.6 to 1.4 equivalents, and further preferably 0.8 to 1.2 equivalents. When the ratio of the active group in the curing agent is less than 0.5 equivalents, it is difficult to obtain sufficient elastic modulus of the obtained cured product. On the other hand, when the ratio of the active group in the curing agent exceeds 1.5 equivalents, there is a tendency for the mechanical strength of the cured shaped body formed from the composite to decrease. However, even in the case where the ratio of the active group in the curing agent is outside the above range, the effects of the present application can be obtained.

[0049] The curing accelerator (catalyst) is not limited as long as it is a composition that accelerates the curing of the epoxy resin by reacting with the epoxy resin. The curing accelerator can be, for example, an imidazole compound such as an alkyl-substituted imidazole or a benzimidazole. The resin composition can have one curing accelerator. The resin composition can also have a plurality of curing accelerators. By having the resin composition contain a curing accelerator, the moldability and the releasability of the composite are easily improved. Also, by having the resin composition contain a curing accelerator, the mechanical strength of the shaped body (for example, an electronic part) manufactured using the composite is improved, or the storage stability of the composite under a high-temperature / high-humidity environment is improved. As a commercially available imidazole-based curing accelerator, for example, at least one selected from the group consisting of 2MZ-H, C11Z, C17Z, 1,2DMZ, 2E4MZ, 2PZ-PW, 2P4MZ, 1B2MZ, 1B2PZ, 2MZ-CN, C11Z-CN, 2E4MZ-CN, 2PZ-CN, C11Z-CNS, 2P4MHZ, TPZ, and SFZ (all manufactured by Shikoku Chemicals Corporation) can be used. As the curing accelerator (catalyst), for example, a urea-based catalyst can be used. As a commercially available urea-based catalyst, for example, U-CAT 3512T manufactured by San-Apro Ltd. can be mentioned.

[0050] The amount of the curing accelerator to be blended is not particularly limited as long as it is an amount that can achieve a curing acceleration effect. However, from the viewpoint of improving the moisture absorption curing property and flowability of the resin composition, the amount of the curing accelerator to be blended can be preferably 0.1 parts by mass or more and 30 parts by mass or less, more preferably 1 part by mass or more and 15 parts by mass or less, based on 100 parts by mass of the epoxy resin. The content of the curing accelerator is preferably 0.001 parts by mass or more and 5 parts by mass or less, based on 100 parts by mass of the total of the epoxy resin and the curing agent (for example, a phenol resin). When the amount of the curing accelerator to be blended is less than 0.1 parts by mass, it is difficult to achieve a sufficient curing acceleration effect. When the amount of the curing accelerator to be blended exceeds 30 parts by mass, the storage stability of the composite is likely to decrease. However, the effects of the present application can be achieved even when the amount and content of the curing accelerator are outside the above ranges.

[0051] The resin composition contains a compound having a siloxane bond (siloxane compound). The siloxane bond is a bond including two silicon atoms (Si) and one oxygen atom (O), and can be represented by -Si-O-Si-. The compound having a siloxane bond can be a polysiloxane compound. The resin composition can contain one siloxane compound, or can contain a plurality of siloxane compounds. From the viewpoint that the molding shrinkage of the composite is likely to decrease and the heat resistance and voltage resistance of the molded body are likely to improve, the resin composition preferably contains a first siloxane compound described later as the siloxane compound. The resin composition can contain only the first siloxane compound as the siloxane compound, or can further contain a second siloxane compound. The resin composition can contain both the first siloxane compound and the second siloxane compound. The resin composition can also contain a siloxane compound other than the first siloxane compound and the second siloxane compound. Hereinafter, the details of the first siloxane compound and the second siloxane compound will be described.

[0052] The first siloxane compound can have a structural unit represented by the following Chemical Formula (1). The structural unit can be simply referred to as "structure". The structural unit represented by the following Chemical Formula (1) is sometimes referred to as "structure unit 1".

[0053]

[0054] In the above Chemical Formula (1), n is an integer of 2 to 200, R 1 and R 2 each independently is an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a monovalent organic group having an epoxy group, a monovalent organic group having a carboxyl group, or a polyalkylene ether group having 3 to 500 carbon atoms.

[0055] The plurality of R1 may be the same as or different from each other. The plurality of R 2 may be the same as or different from each other. R 1 may be the same as or different from each other. R 2 may be the same as or different from each other. The first siloxane compound can have a repeating unit represented by the above Chemical Formula (1).

[0056] From the viewpoint that the molding shrinkage of the composite is easily reduced and the heat resistance and voltage resistance of the molded body are easily improved, the first siloxane compound is preferably a compound represented by the following Chemical Formula (2). The structural unit represented by the following Chemical Formula (2) is sometimes referred to as "Structural Unit 2".

[0057]

[0058] In the above Chemical Formula (2), R 3 is an alkylene group having 1 to 10 carbon atoms.

[0059] The first siloxane compound can have a plurality of Structural Unit 2. The plurality of R 3 may be the same as or different from each other. The first siloxane compound can have a repeating unit represented by the above Chemical Formula (2).

[0060] From the viewpoint that the molding shrinkage of the composite is easily reduced and the heat resistance and voltage resistance of the molded body are easily improved, the first siloxane compound is preferably a compound represented by the following Chemical Formula (3). The compound represented by the following Chemical Formula (3) is sometimes referred to as "Compound 3".

[0061]

[0062] In the above Chemical Formula (3), n is an integer of 2 to 200. m1 and m2 are each independently an integer of 1 to 200. R 4 , R 5 , R 6 , and R 7 are each independently an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a monovalent organic group having an epoxy group, a monovalent organic group having a carboxyl group, or a polyalkylene ether group having 3 to 500 carbon atoms. R 8 and R 9 are each independently an alkylene group having 1 to 10 carbon atoms. R 10 and R 11 are each independently a divalent hydrocarbon group having 1 to 10 carbon atoms which can include an ether structure. R 10 and R 11may be a divalent hydrocarbon group having 1 to 10 carbon atoms which can contain an oxygen atom or which can be bonded via an oxygen atom.

[0063] the plurality of R 4 may be the same as or different from each other. the plurality of R 5 may be the same as or different from each other. R 4 , R 5 , R 6 , and R 7 may be the same as or different from each other. the plurality of R 8 may be the same as or different from each other. the plurality of R 9 may be the same as or different from each other. R 8 , and R 9 may be the same as or different from each other. The weight average molecular weight (Mw) of the compound 3 may be, for example, 4000 or more and 20000 or less.

[0064] The commercially available product of the compound 3 may be, for example, DBL-C31, DBL-C32, or the like manufactured by Gelest, Inc.

[0065] From the viewpoint that the molding shrinkage of the composite is easily reduced and the heat resistance and voltage resistance of the molded body are easily improved, the second siloxane compound is preferably a structural unit represented by the following formula (4) and a structural unit represented by the following formula (5). The structural unit represented by the following formula (4) is sometimes referred to as "structural unit 4". The structural unit represented by the following formula (5) is sometimes referred to as "structural unit 5".

[0066]

[0067] In the above formula (4), R 12 is a monovalent hydrocarbon group having 1 to 12 carbon atoms. R 17 is an organic group having 1 or more carbon atoms.

[0068] R 12 may be, for example, an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, an isobutyl group, a tert-butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a 2-ethylhexyl group, or the like; an alkenyl group such as a vinyl group, an allyl group, a butenyl group, a pentenyl group, a hexenyl group, or the like; an aryl group such as a phenyl group, a tolyl group, a xylyl group, a naphthyl group, a biphenyl group, or the like; an aralkyl group such as a benzyl group, a phenethyl group, or the like. R 12 is preferably a methyl group or a phenyl group.

[0069] The second siloxane compound can have a plurality of structural units 4. The plurality of R 12may be the same as or different from each other. The 2nd siloxane compound can have a repeating unit represented by the above Chemical Formula (4).

[0070]

[0071] In the above Chemical Formula (5), R 13 and R 14 are each independently a monovalent hydrocarbon group having 1 to 12 carbon atoms.

[0072] R 13 For example, it can be an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, an isobutyl group, a tert-butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a 2-ethylhexyl group, and the like; an alkenyl group such as a vinyl group, an allyl group, a butenyl group, a pentenyl group, a hexenyl group, and the like; an aryl group such as a phenyl group, a tolyl group, a xylyl group, a naphthyl group, a biphenyl group, and the like; an aralkyl group such as a benzyl group, a phenethyl group, and the like. R 13 Preferably, it is a methyl group or a phenyl group.

[0073] R 14 For example, it can be an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, an isobutyl group, a tert-butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a 2-ethylhexyl group, and the like; an alkenyl group such as a vinyl group, an allyl group, a butenyl group, a pentenyl group, a hexenyl group, and the like; an aryl group such as a phenyl group, a tolyl group, a xylyl group, a naphthyl group, a biphenyl group, and the like; an aralkyl group such as a benzyl group, a phenethyl group, and the like. R 14 Preferably, it is a methyl group or a phenyl group.

[0074] The 2nd siloxane compound can have a plurality of structural units 5. The plurality of R 13 may be the same as or different from each other. The plurality of R 14 may be the same as or different from each other. R 13 and R 14 may be the same as or different from each other. The 2nd siloxane compound can have a repeating unit represented by the above Chemical Formula (5).

[0075] From the viewpoint of storage stability of the 2nd siloxane compound, the end of the molecule of the 2nd siloxane compound is preferably any one of R 12 , R 13 , R 14 , a hydroxyl group, and an alkoxy group. The alkoxy group can be, for example, a methoxy group, an ethoxy group, a propoxy group, or a butoxy group.

[0076] From the viewpoint of easily reducing the molding shrinkage of the composite and easily improving the heat resistance and voltage resistance of the molded body, the 2nd siloxane compound is preferably a structural unit represented by the following Chemical Formula (6). The structural unit represented by the following Chemical Formula (6) is sometimes referred to as “structural unit 6”.

[0077]

[0078] In the above formula (6), R 15 is a monovalent hydrocarbon group having 1 to 12 carbon atoms. R 16 is a monovalent organic group having an epoxy group.

[0079] R 15 For example, it can be an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, an isobutyl group, a tert-butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a 2-ethylhexyl group, and the like; an alkenyl group such as a vinyl group, an allyl group, a butenyl group, a pentenyl group, a hexenyl group, and the like; an aryl group such as a phenyl group, a tolyl group, a xylyl group, a naphthyl group, a biphenyl group, and the like; an aralkyl group such as a benzyl group, a phenethyl group, and the like. R 13 Preferably, it is a methyl group or a phenyl group.

[0080] R 16 For example, it can be a 2,3-epoxypropyl group, a 3,4-epoxybutyl group, a 4,5-epoxypentyl group, a 2-epoxypropoxyethyl group, a 3-epoxypropoxypropyl group, a 4-epoxypropoxybutyl group, a 2-(3,4-epoxycyclohexyl)ethyl group, a 3-(3,4-epoxycyclohexyl)propyl group, and the like. R 16 Preferably, it is a 3-epoxypropoxypropyl group.

[0081] The 2nd siloxane compound can have a plurality of structural units 6. The plurality of R 15 may be the same as or different from each other. The plurality of R 16 may be the same as or different from each other. The 2nd siloxane compound can have a repeating unit represented by the above formula (6).

[0082] From the viewpoint that the molding shrinkage of the composite is easily reduced and the heat resistance and voltage resistance of the molded body are easily improved, the 2nd siloxane compound is preferably a compound having at least one structural unit selected from the group consisting of a structural unit represented by the following formula (7), a structural unit represented by the following formula (8), a structural unit represented by the following formula (9), and a structural unit represented by the following formula (10). The structural unit represented by the following formula (7) is sometimes referred to as "structural unit 7". The structural unit represented by the following formula (8) is sometimes referred to as "structural unit 8". The structural unit represented by the following formula (9) is sometimes referred to as "structural unit 9". The structural unit represented by the following formula (10) is sometimes referred to as "structural unit 10". A compound having at least one structural unit selected from the group consisting of the above structural unit 7, structural unit 8, structural unit 9, and structural unit 10 is sometimes referred to as "compound 11". The compound 11 can have all of the structural unit 7, structural unit 8, structural unit 9, and structural unit 10.

[0083]

[0084] In the above formula (9), R 18 is an organic group having 1 or more carbon atoms.

[0085]

[0086] In the above formula (10), R 19 is an organic group having 1 or more carbon atoms.

[0087] Compound 11 can have a plurality of structural units 7. Compound 11 can have a repeating unit represented by the above formula (7). Compound 11 can have a plurality of structural units 8. Compound 11 can have a repeating unit represented by the above formula (8). Compound 11 can have a plurality of structural units 9. Compound 11 can have a repeating unit represented by the above formula (9). Compound 11 can have a plurality of structural units 10. Compound 11 can have a repeating unit represented by the above formula (10).

[0088] A commercially available product of compound 11 can be, for example, AY42-119 manufactured by Dow Corning Toray Co., Ltd.

[0089] The epoxy equivalent weight of the second siloxane compound can be 500 or more and 4000 or less or 1000 or more and 2500 or less. When the epoxy equivalent weight is within the above range, the flowability of the composite is easily improved, and the moldability is easily improved.

[0090] The softening point of the second siloxane compound is preferably 40°C or more and 120°C or less, and more preferably 50°C or more and 100°C or less. When the softening point is within the above range, the mechanical strength of the molded body formed from the composite is easily improved. The softening point of the second siloxane compound can be adjusted depending on the molecular weight, the structure (for example, the content ratio of each structural unit), the type of the organic group bonded to the silicon atom, and the like of the second siloxane compound. From the viewpoint of improving the flowability of the composite, it is preferable to adjust the softening point depending on the content of the aryl group in the second siloxane compound. The aryl group can be, for example, a phenyl group, a tolyl group, a xylyl group, a naphthyl group, a biphenyl group, or the like. The aryl group is preferably a phenyl group. It is more preferable to adjust the softening point depending on the content of the phenyl group in the monovalent organic group bonded to the silicon atom in the second siloxane compound. The content of the above phenyl group can be adjusted to be preferably 60 mol% or more and 100 mol% or less, and more preferably 70 mol% or more and 85 mol% or less.

[0091] The weight average molecular weight (Mw) of the second siloxane compound can be 1000 or more and 30000 or less, preferably 2000 or more and 20000 or less, more preferably 3000 or more and 10000 or less. The weight average molecular weight (Mw) can be measured by gel permeation chromatography (GPC), and can be a value converted using a standard polystyrene calibration curve. The second siloxane compound is preferably a random copolymer.

[0092] The resin composition can contain one of the above-described siloxane compounds, or can contain a plurality of the above-described siloxane compounds.

[0093] The coupling agent improves the adhesiveness of the resin composition to the metal element-containing particles that constitute the metal element-containing powder, and improves the flexibility and mechanical strength of the molded body formed from the composite. The coupling agent can be, for example, at least one selected from the group consisting of a silane-based compound (silane coupling agent), a titanium-based compound, an aluminum compound (aluminum chelate-based), and an aluminum / zirconium-based compound. The silane coupling agent can be, for example, at least one selected from the group consisting of an epoxy silane, a mercapto silane, an amino silane, an alkyl silane, an ureido silane, an acid anhydride-based silane, and a vinyl silane. In particular, a silane coupling agent of an amino phenyl type is preferred. The resin composition can contain one of the above-described coupling agents, or can contain a plurality of the above-described coupling agents.

[0094] For environmental safety, recyclability, moldability, and low cost of the composite, the composite can include a flame retardant. The flame retardant can be, for example, at least one selected from the group consisting of a bromine-based flame retardant, a bulb flame retardant, a hydrated metal compound-based flame retardant, a silicone-based flame retardant, a nitrogen-containing compound, a hindered amine compound, an organic metal compound, and an aromatic engineering plastic. The resin composition can contain one of the above-described flame retardants, or can contain a plurality of the above-described flame retardants.

[0095] When a molded body is formed from the composite using a mold, the resin composition can contain a wax. The wax improves the flowability of the composite when the composite is molded (for example, transfer molding), and functions as a mold release agent. The wax can be at least any one of a higher fatty acid such as a fatty acid and a fatty acid ester.

[0096] The wax may be, for example, at least one selected from the group consisting of lignoceric acid, stearic acid, 12-oxystearic acid, lauric acid, and the like fatty acids or esters of these; zinc stearate, calcium stearate, barium stearate, aluminum stearate, magnesium stearate, calcium laurate, zinc linoleate, calcium ricinoleate, zinc 2-ethylhexanoate, and the like fatty acid salts; stearic acid amide, oleic acid amide, erucic acid amide, behenic acid amide, palmitic acid amide, lauric acid amide, hydroxystearic acid amide, methylenebisstearic acid amide, ethylenebisstearic acid amide, ethylenebislauric acid amide, distearyladipic acid amide, ethylenebisoelic acid amide, N-steryl stearic acid amide, N-oleyl stearic acid amide, N-steryl erucic acid amide, hydroxymethyl stearic acid amide, hydroxymethyl behenic acid amide, and the like fatty acid amides; butyl stearate and the like fatty acid esters; ethylene glycol, stearyl alcohol, and the like alcohols; polyethers including polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and modifications of these; silicone compounds such as silicone oil, silicone grease, and the like; fluorinated compounds such as fluorine-based oil, fluorine-based grease, fluorine-containing resin powder, and the like; and waxes such as paraffin wax, polyethylene wax, amide wax, polypropylene wax, ester wax, carnauba, micro wax, and the like. As a commercially available product of lignoceric acid ester, for example, LICOWAX-OP manufactured by Clariant Chemicals Co., Ltd. can be given. As a commercially available product of natural wax, for example, Carnauba wax No. 1 manufactured by CERARICA NODA Co., Ltd. can be given.

[0097] Further, as the release agent, for example, metal soaps constituted by bonding of long-chain fatty acids such as lignoceric acid, stearic acid, 12-oxystearic acid, lauric acid, and the like with metals can be given. As a commercially available product of metal soap, for example, Powder Base L manufactured by NOF CORPORATION, and the like can be given.

[0098] (Powder containing a metal element)

[0099] The metal element-containing powder (metal element-containing particle) can contain, for example, at least one selected from the group consisting of a metal monomer, an alloy, and a metal compound. The metal element-containing powder can include, for example, at least one selected from the group consisting of a metal monomer, an alloy, and a metal compound. The alloy can include at least one selected from the group consisting of a solid solution, a eutectic, and an intermetallic compound. The alloy can be, for example, stainless steel (Fe-Cr-based alloy, Fe-Ni-Cr-based alloy, or the like). The metal compound can be, for example, wustite or the like oxide. The metal element-containing powder can include one metal element or a plurality of metal elements. The metal element included in the metal element-containing powder can be, for example, a base metal element, a noble metal element, a transition metal element, or a rare earth element. The composite can include one metal element-containing powder or a plurality of metal element-containing powders having different compositions.

[0100] The metal element-containing powder is not limited to the above composition. The metal element included in the metal element-containing powder can be, for example, at least one selected from the group consisting of 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), praseodymium (Pr), neodymium (Nd), samarium (Sm), and dysprosium (Dy). The metal element-containing powder can further include an element other than a metal element. The metal element-containing powder can include, for example, oxygen (O), beryllium (Be), phosphorus (P), boron (B), or silicon (Si). The metal element-containing powder can be a magnetic powder. The metal element-containing powder can be a soft magnetic alloy or a hard magnetic alloy. The metal element-containing powder can be, for example, at least one magnetic powder selected from the group consisting of an Fe-Si-based alloy, an Fe-Si-Al-based alloy (sendust), an Fe-Ni-based alloy (permalloy), an Fe-Cu-Ni-based alloy (high permeability alloy), an Fe-Co-based alloy (permendur), an Fe-Cr-Si-based alloy (electromagnetic stainless steel), an Nd-Fe-B-based alloy (rare earth magnet), an Sm-Fe-N-based alloy (rare earth magnet), an Al-Ni-Co-based alloy (alnico), and wustite. The wustite can be spinel wustite, hexagonal wustite, or garnet wustite. The metal element-containing powder can also be a copper alloy such as a Cu-Sn-based alloy, a Cu-Sn-P-based alloy, a Cu-Ni-based alloy, or a Cu-Be-based alloy. The metal element-containing powder can include one of the above elements and compositions or a plurality of the above elements and compositions.

[0101] The metal element-containing powder can also be Fe monomer. The metal element-containing powder can also be an alloy containing iron (Fe-based alloy). The Fe-based alloy can be, for example, an Fe-Si-Cr-based alloy or an Nd-Fe-B-based alloy. The metal element-containing powder can also be at least any one of amorphous iron powder and carbonyl iron powder. When the metal element-containing powder contains at least any one of Fe monomer and an Fe-based alloy, a molded body having a high space factor and excellent magnetic properties is easily produced from the composite. The metal element-containing powder can also be an Fe amorphous alloy. As a commercially available product of the Fe amorphous alloy powder, for example, at least one selected from the group consisting of AW2-08, KUAMET-6B2, KUAMET 9A4-II (trade names manufactured by Epson Atmix Corporation), DAP MS3, DAP MS7, DAP MSA10, DAP PB, DAP PC, DAP MKV49, DAP 410L, DAP 430L, DAP HYB series (trade names manufactured by Daido Steel Co., Ltd.), MH45D, MH28D, MH25D, and MH20D (trade names manufactured by Kobe Steel, Ltd.) can be used.

[0102] <Method for producing the composite>

[0103] In the production of the composite, the metal element-containing powder and the resin composition (each component constituting the resin composition) are mixed while being heated. For example, the metal element-containing powder and the resin composition can be mixed while being heated using a kneader, a roll, a blender, or the like. By the heating and mixing of the metal element-containing powder and the resin composition, the resin composition coats the metal element-containing particles constituting the metal element-containing powder, partially or entirely, and a part or all of the epoxy resin in the resin composition becomes a semi-cured product. As a result, the composite is obtained. The composite can also be obtained by further adding a wax to the powder obtained by the heating and mixing of the metal element-containing powder and the resin composition. The resin composition and the wax can also be mixed in advance.

[0104] In the kneading, the powder containing the metal element, the siloxane compound, the epoxy resin, the curing agent, the curing accelerator, and the coupling agent can be kneaded in the tank. The epoxy resin, the curing agent, and the curing accelerator can be put into the tank after the powder containing the metal element, the siloxane compound, and the coupling agent are mixed in the tank. The siloxane compound, the epoxy resin, the curing agent, and the coupling agent can be kneaded in the tank, and then the curing accelerator can be put into the tank to further knead the materials in the tank. A mixed powder of the epoxy resin, the curing agent, and the curing accelerator (resin mixed powder) can be prepared in advance, and then the powder containing the metal element, the siloxane compound, and the coupling agent can be kneaded to prepare a metal mixed powder, and then the metal mixed powder and the resin mixed powder can be kneaded.

[0105] The kneading time also depends on the type of the kneading machine, the volume of the kneading machine, and the production amount of the composite, and is preferably 1 minute or more, more preferably 2 minutes or more, and further preferably 3 minutes or more. Furthermore, the kneading time is preferably 20 minutes or less, more preferably 15 minutes or less, and further preferably 10 minutes or less. When the kneading time is less than 1 minute, the kneading is insufficient, the moldability of the composite is impaired, and the degree of curing of the composite is deviated. When the kneading time exceeds 20 minutes, the fluidity and the moldability of the composite are easily impaired, for example, by the curing of the resin composition (for example, the epoxy resin and the phenol resin) in the tank. When the materials in the tank are kneaded with the kneader while being heated, the heating temperature can be, for example, a temperature at which a semi-cured product of the epoxy resin (a B-stage epoxy resin) is generated and the generation of a cured product of the epoxy resin (a C-stage epoxy resin) is suppressed. The heating temperature can also be a temperature lower than the activation temperature of the curing accelerator. The heating temperature is preferably 50°C or higher, more preferably 60°C or higher, and further preferably 70°C or higher. The heating temperature is preferably 150°C or lower, more preferably 120°C or lower, and further preferably 110°C or lower. When the heating temperature is within the above range, the resin composition in the tank is softened and easily coats the surfaces of the metal element-containing particles constituting the powder containing the metal element, so that the semi-cured product of the epoxy resin is easily generated, and the complete curing of the epoxy resin in the kneading is easily suppressed.

[0106] <Shaped body>

[0107] The shaped body of the present embodiment can include the above-described composite. The shaped body can include at least one selected from the group consisting of an uncured resin composition, a semi-cured product of the resin composition (a B-stage resin composition), and a cured product of the resin composition (a C-stage resin composition). The shaped body can be a cured product of the above-described composite.

[0108] <Method for producing a shaped body>

[0109] The method for producing the shaped body of the present embodiment can include a step of pressurizing the composite in a mold. The method for producing the shaped body can include only the step of pressurizing the composite in a mold, or can include other steps in addition to the step. The method for producing the shaped body can include a first step, a second step, and a third step. Details of each step are described below.

[0110] In the first step, the composite is produced by the above method.

[0111] In the second step, the shaped body (a shaped body in the B stage) is obtained by pressurizing the composite in a mold. Here, the resin composition is filled between each metal element-containing particle that constitutes the metal element-containing powder. Also, the resin composition functions as a binding material (binder) that bonds the metal element-containing particles to each other.

[0112] As the second step, transfer molding of the composite can also be performed. In the transfer molding, the composite can be pressurized at a pressure of 5 MPa or higher and 50 MPa or lower. The higher the molding pressure, the more likely it is that a shaped body having excellent mechanical strength will be obtained. When the productivity of the shaped body and the life of the mold are taken into consideration, the molding pressure is preferably 8 MPa or higher and 20 MPa or lower. The density of the shaped body formed by the transfer molding, relative to the true density of the composite, can be preferably 75% or higher and 86% or lower, and more preferably 80% or higher and 86% or lower. When the density of the shaped body is 75% or higher and 86% or lower, a shaped body having excellent mechanical strength is easily obtained. In the transfer molding, the second step and the third step can also be performed collectively.

[0113] In the third step, the shaped body is cured by heat treatment to obtain a C-stage shaped body. Since the composite of the present embodiment contains the siloxane compound as one of the elastomers, the elasticity of the entire composite is reduced, and the stress acting on the composite is reduced as the composite shrinks (thermally cures) upon shaping. As a result, the shrinkage of the composite upon shaping is reduced in the process of forming the shaped body by thermal curing of the composite. Also, as described above, the mechanism is not clear, but since the composite of the present embodiment contains the siloxane compound as one of the elastomers in a prescribed amount, the heat resistance and voltage resistance of the shaped body obtained from the composite are improved. The temperature of the heat treatment can be any temperature at which the resin composition in the shaped body is sufficiently cured. The temperature of the heat treatment can be preferably 100°C or higher and 300°C or lower, and more preferably 110°C or higher and 250°C or lower. In order to suppress oxidation of the metal element-containing powder in the shaped body, it is preferable to perform the heat treatment in an inert atmosphere. When the heat treatment temperature exceeds 300°C, the metal element-containing powder is oxidized or the resin cured product is deteriorated due to the trace amount of oxygen inevitably contained in the atmosphere of the heat treatment. In order to suppress oxidation of the metal element-containing powder and deterioration of the resin cured product and to sufficiently cure the resin composition, the holding time of the heat treatment temperature can be preferably several minutes or more and 10 hours or less, and more preferably 3 minutes or more and 8 hours or less.

[0114] Example

[0115] Hereinafter, the present application will be further explained in detail by examples and comparative examples, but the present application is not limited to any of these examples.

[0116] (Example 1)

[0117] [Preparation of the composite]

[0118] Into a plastic (poly) container, 50 g of biphenyl aralkyl type epoxy resin, 50 g of multifunctional type epoxy resin, 14.5 g of phenol novolak resin 1 (curing agent), 23.6 g of phenol novolak resin 2 (curing agent), 5.9 g of urea-based catalyst (curing accelerator), 7.5 g of zinc laurate type metal soap (mold release agent), 2.0 g of montanic acid ester (mold release agent (wax)), and 4.0 g of natural wax (mold release agent (wax)) were put. A resin mixture was prepared by mixing these raw materials in the plastic container for 10 minutes. The resin mixture corresponds to all the components in the resin composition except for the siloxane compound and the coupling agent.

[0119] As the biphenyl aralkyl type epoxy resin, NC-3000 manufactured by Nippon Kayaku Co., Ltd. was used.

[0120] As the multifunctional epoxy resin, VG-3101L manufactured by Printec Corporation was used.

[0121] As the phenol novolak resin 1, HF-3M manufactured by Meiwa Plastic Industries, Ltd. was used.

[0122] As the phenol novolak resin 2, MEW-1800 manufactured by Meiwa Plastic Industries, Ltd. was used.

[0123] As the urea-based catalyst, U-CAT 3512T manufactured by San-Apro Ltd. was used.

[0124] As the zinc laurate-based metal soap, Powder Base L manufactured by NOF CORPORATION was used.

[0125] As the montanic acid ester, LICOWAX-OP manufactured by Clariant Chemicals Co., Ltd. was used.

[0126] As the natural wax, Carnauba wax No. 1 manufactured by CERARICA NODA Co., Ltd. was used.

[0127] The amorphous iron powder 1 and the amorphous iron powder 2 were uniformly mixed for 5 minutes with a pressurized double screw kneader (manufactured by Nihon Spindle Manufacturing Co., Ltd., capacity 5 L) to prepare 3741 g of a metal element-containing powder. The content of the amorphous iron powder 1 in the metal element-containing powder was 82 mass%. The content of the amorphous iron powder 2 in the metal element-containing powder was 18 mass%. 1.9 g of methacryloxyoctyltrimethoxysilane (coupling agent), 1.9 g of 3-mercaptopropyltrimethoxysilane (coupling agent), and 15 g of caprolactone-modified dimethyl silicone (compound having a siloxane bond) were added to the metal element-containing powder in the double screw kneader. Subsequently, the contents of the double screw kneader were heated to 90°C, and while maintaining the temperature, the contents of the double screw kneader were mixed for 10 minutes. Subsequently, the above resin mixture was added to the contents of the double screw kneader, and while maintaining the temperature of the contents at 120°C, the contents were melt / kneaded for 15 minutes. After the kneadate obtained by the above melt / kneading was cooled to room temperature, the kneadate was pulverized with a hammer so that the kneadate had a prescribed particle size. In addition, the above "melt" refers to the melting of at least a part of the resin composition in the contents of the double screw kneader. The metal element-containing powder in the composite does not melt during the preparation of the composite.

[0128] As the amorphous iron powder 1, KUAMET 9A4-II053C03 (average particle diameter 24 μm) manufactured by Epson Atmix Corporation was used.

[0129] As the amorphous iron powder 2, AW2-08 (average particle diameter 5.3 μm) manufactured by Epson Atmix Corporation was used.

[0130] As the methacryloxyoctyltrimethoxysilane, KBM-5803 manufactured by Shin-Etsu Chemical Co., Ltd. was used.

[0131] As the 3-mercaptopropyltrimethoxysilane, KBM-803 manufactured by Shin-Etsu Chemical Co., Ltd. was used.

[0132] As the caprolactone-modified dimethyl silicone, DBL-C32 manufactured by Gelest, Inc. was used. The caprolactone-modified dimethyl silicone is a compound represented by the above Chemical Formula (3).

[0133] The composite of Example 1 was prepared by the above method. The content of the powder containing a metal element in the composite was 95.5 mass%.

[0134] (Other Examples and Comparative Examples)

[0135] The composites of the other examples and comparative examples were produced in the same manner as in Example 1 except that the raw material prescription was changed as shown in Table 1. The evaluation relating to the composite of each example was performed by the same method as in Example 1. In addition, KBM-403 described in Table 1 is 3-glycidoxypropyltrimethoxysilane manufactured by Shin-Etsu Chemical Co., Ltd.

[0136] [Evaluation]

[0137] The following evaluation was performed using the composites of each example and comparative example. The results are shown in Table 1.

[0138] (Evaluation of heat resistance: 250°C bending test)

[0139] After the composites of each example and comparative example were transfer molded under the conditions of a molding die temperature of 175°C, a molding pressure of 13.5 MPa, and a curing time of 360 seconds, post curing at 175°C for 5.5 hours was performed, whereby test pieces were obtained. The size of the test pieces was 80 mm in length, 10 mm in width, and 3.0 mm in thickness.

[0140] The test pieces were subjected to a three-point support type bending test using an Autograph with a constant temperature tank. As the Autograph, AGS-500A manufactured by Shimadzu Corporation was used. The temperature of the constant temperature tank was 250°C. In the bending test, one face of the test piece was supported by two support points. A load was applied to the center position between the two support points on the other face of the test piece. The load at the time when the test piece was broken was measured. The measurement conditions of the bending test were as follows.

[0141] Distance Lv between the two support points: 64.0 ± 0.5 mm

[0142] Head speed: 2.0 ± 0.2 mm / minute

[0143] Chart speed: 100 mm / minute

[0144] Chart full scale: 490 N (50 kgf)

[0145] The bending strength σ (unit: MPa) was calculated according to the following mathematical expression (A). The bending elastic modulus E (unit: GPa) was calculated according to the following mathematical expression (B). The bending elongation ε (unit: %) was calculated according to the following mathematical expression (C). In the following mathematical expressions, "P" is the load at the time when the test piece was broken (unit: N). "Lv" is the distance between the two support points (unit: mm). "W" is the lateral width of the test piece (unit: mm). "t" is the thickness of the test piece (unit: mm). "F / Y" is the slope of the straight line portion of the load-deflection curve (unit: N / mm). "s" is the deflection of the test piece just before the test piece was broken (unit: mm).

[0146] σ = (3 x P x Lv) / (2 x W x t 2 ) (A)

[0147] E = [Lv 3 / (4 x W x t 3 )] x (F / Y) (B)

[0148] ε = (600 x s x t) / Lv 2 (C)

[0149] (Evaluation of voltage resistance: voltage resistance test)

[0150] After the transfer molding of the compounds of each of the examples and comparative examples was performed at a molding die temperature of 175°C, a molding pressure of 13.5 MPa, and a curing time of 360 seconds, post-curing was performed at 175°C for 5.5 hours, whereby test pieces having a thickness of 2.0 mm were produced.

[0151] When the voltage resistance test was performed, a stainless steel plate to which a ground wire was connected, a conductive rubber plate, a test piece, and a 10 mm diameter stainless steel electrode to which a high voltage wire was connected were sequentially arranged on the insulating plate. The high voltage wire and the ground wire were connected to a high voltage output terminal and a ground terminal of a high voltage amplifier, respectively. A waveform output of a function generator was input to the high voltage amplifier to generate a test voltage in such a manner that the voltage was raised at a rate of 10 V per second from 0 V to a maximum of 2000 V, and was applied to the test piece. The voltage at the time when the current through the test piece exceeded 10 mA was read. Subsequently, a stainless steel electrode was arranged at a different position on the test piece, and a voltage was applied thereto in the same manner. This was repeated a predetermined number of times, and the average of the read voltages was taken as the voltage resistance (insulation breakdown voltage: V / mm) of the test piece.

[0152] [Table 1]

[0153]

[0154] Industrial applicability

[0155] The composite of the present application can obtain a molded body having both heat resistance and voltage resistance, and thus has high industrial value.

Claims

1. A composite having a powder containing a metal element and a resin composition, the resin composition containing an epoxy resin and a compound having a siloxane bond, a content of the compound having a siloxane bond is 20 parts by mass or less relative to 100 parts by mass of the epoxy resin, the composite contains a compound represented by the following formula (3) as the siloxane compound, In the formula (3), n is an integer of 2 to 200, each of m1 and m2 is independently an integer of 1 to 200, each of R 4 , R 5 , R 6 , and R 7 is independently an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a monovalent organic group having an epoxy group, a monovalent organic group having a carboxyl group, or a polyalkylene ether group having 3 to 500 carbon atoms, each of R 8 and R 9 is independently an alkylene group having 1 to 10 carbon atoms, each of R 10 and R 11 is independently a divalent hydrocarbon group having 1 to 10 carbon atoms which can include an ether structure.

2. The composite according to claim 1, which contains at least one of a biphenylene aralkyl type epoxy resin and an isocyanate-modified epoxy resin as the epoxy resin.

3. The composite according to claim 1 or 2, wherein, a content of the powder containing a metal element is 90 mass% or more and less than 100 mass%.

4. A shaped body having the composite according to any one of claims 1 to 3.

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