TW202128875A - Compound and molded object - Google Patents

Abstract

A compound comprising a metallic-element-containing powder and a resin composition, wherein the resin composition comprises an epoxy resin and one or more compounds each having a siloxane bond, the compounds having a siloxane bond being contained in an amount of 20 parts by mass or less per 100 parts by mass of the epoxy resin and including a siloxane compound having a structure represented by chemical formula (1).

Description

Composites and shaped bodies

The present invention relates to a composite and formed body.

Compounds containing metal powder and resin composition are used as raw materials for various industrial products such as inductors, electromagnetic shields, or bonded magnets based on the various physical properties of metal powders (see below) Patent Document 1.)

[Patent Document 1] JP 2014-13803 A

Sometimes industrial products such as inductors require resistance to heat or voltage. The object of the present invention is to provide a composite capable of obtaining a molded body having heat resistance and voltage resistance at the same time, and a molded body provided with the composite.

[前述化學式（1）中，n為2～200的整數，R¹ 及R² 各自獨立地為碳數1～10的烷基、碳數6～10的芳基、碳數1～10的烷氧基、具有環氧基之1價的有機基、具有羧基之1價的有機基或碳數3～500的聚伸烷基醚基。]The composite of one aspect of the present invention includes a powder containing a metal element and a resin composition. The resin composition contains an epoxy resin and a chemical compound having a siloxane bond. The content of the compound having a siloxane bond is relative to 100 parts by mass of the epoxy resin is 20 parts by mass or less, and the compound having a siloxane bond includes a siloxane compound having a structure represented by the following chemical formula (1). [Chemical formula 1]

[In the aforementioned chemical formula (1), n is an integer of 2 to 200, and R ¹ and R ² are each independently an alkyl group having 1 to 10 carbons, an aryl group having 6 to 10 carbons, and an alkane having 1 to 10 carbons. An oxy group, 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 carbons. ]

In the above-mentioned compound of one aspect of the present invention, the siloxane compound may further have a structural unit represented by the following chemical formula (2).

[前述化學式（2）中，R³ 為碳數1～10的伸烷基。][Chemical formula 2]

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

The above-mentioned compound of one aspect of the present invention may include a compound represented by the following chemical formula (3) as a siloxane compound.

[前述化學式（3）中，n為2～200的整數，m₁ 及m₂ 各自獨立地為1～200的整數，R⁴ 、R⁵ 、R⁶ 及R⁷ 各自獨立地為碳數1～10的烷基、碳數6～10的芳基、碳數1～10的烷氧基、具有環氧基之1價的有機基、具有羧基之1價的有機基或碳數3～500的聚伸烷基醚基，R⁸ 及R⁹ 各自獨立地為碳數1～10的伸烷基，R¹⁰ 及R¹¹ 各自獨立地為可以包含醚結構之碳數1～10的2價的烴基。][Chemical formula 3]

[In the aforementioned chemical formula (3), n is an integer of 2 to 200, m ₁ and m ₂ are each independently an integer of 1 to 200, and R ⁴ , R ⁵ , R ⁶ and R ⁷ are each independently a carbon number of 1 to 10 alkyl groups, aryl groups having 6 to 10 carbons, alkoxy groups having 1 to 10 carbons, monovalent organic groups having epoxy groups, monovalent organic groups having carboxyl groups, or those having 3 to 500 carbons Polyalkylene ether group, R ⁸ and R ⁹ are each independently an alkylene group having 1 to 10 carbons, and R ¹⁰ and R ¹¹ are each independently a divalent hydrocarbon group having 1 to 10 carbons that may include an ether structure . ]

The above-mentioned compound of one aspect of the present invention may include at least one of a biphenylene aralkyl type epoxy resin and an isocyanate modified epoxy resin as an epoxy resin.

In the aforementioned composite of one aspect of the present invention, the content of the metal element-containing powder may be 90% by mass or more and less than 100% by mass.

The molded body of one aspect of the present invention includes the above-mentioned composite. [Effects of the invention]

According to the present invention, there is provided a composite capable of obtaining a molded body having heat resistance and voltage resistance at the same time, and a molded body provided with the composite.

Hereinafter, preferred embodiments of the present invention will be described. However, the present invention is not limited at all by the following embodiments.

＜Overview of the compound＞ The composite of this embodiment includes a metal element-containing powder and a resin composition. The metal-containing powder is composed of multiple (mostly) metal-containing particles. The metal element-containing powder (metal element-containing particle) may contain, for example, at least one selected from the group consisting of metal monomers, alloys, and metal compounds. The resin composition contains at least an epoxy resin and a compound having a siloxane bond. Compounds with siloxane bonds are sometimes referred to as "siloxane compounds". In addition to the epoxy resin and the silicone compound, the resin composition may also contain other components. For example, the resin composition may contain a curing agent. The resin composition may contain a hardening accelerator. The resin composition may also contain additives. The resin composition may be a component capable of containing an epoxy resin, a silicone compound, a hardener, a hardening accelerator, and an additive, and may be a remaining component (non-volatile component) other than the organic solvent and the powder containing the metal element. The additive is a component of the resin composition excluding the remaining part of the resin, silicone compound, hardener, and hardening accelerator. The additives are, for example, coupling agents or flame retardants. The resin composition may contain wax as an additive. The composite may be a powder (composite powder).

The composite of this embodiment contains a silicone compound as an elastomer in a predetermined amount. Although the reason why the heat resistance and the voltage resistance of the molded body obtained from the composite are improved by the predetermined amount of the silicone compound is not clear, the inventors speculate the following possibility. First, it is considered that the addition of the silicone compound improves the fluidity of the contained components and suppresses the generation of internal voids during molding. Second, it is believed that the low compatibility between the metal-containing powder and the epoxy resin causes the degradation of characteristics from the interface between the two. However, the addition of a silicone compound can improve the compatibility of the two. However, the effects of the present invention are not limited to the above-mentioned matters.

The composite may include a metal element-containing powder and a resin composition attached to the surface of each metal element-containing particle constituting the metal element-containing powder. The resin composition may cover the entire surface of the particle or only a part of the surface of the particle. The composite may also have an unhardened resin composition and powder containing metal elements. The composite may also include a semi-hardened resin composition (for example, a B-stage resin composition) and powders containing metal elements. The composite may include both an uncured resin composition and a semi-cured resin composition. The composite can also be composed of a powder containing metal elements and a resin composition.

The content of the metal element-containing powder in the composite can be 90% by mass or more and less than 100% by mass, 90% by mass or more and 99.8% by mass or less, 92% by mass or more and 99.5% by mass or less relative to the mass of the entire composite. , 94% by mass or more and 98.5% by mass or less or 94% by mass or more and 97.5% by mass or less. In addition to the powder containing metal elements, the composite may also contain other filler materials (for example, silica filler).

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

The content of the silicone compound in the composite is 20 parts by mass or less with respect to 100 parts by mass of the epoxy resin, but may be 17.5 parts by mass or less, or 15 parts by mass or less. When the content of the siloxane compound is within the above-mentioned range, the heat resistance and the voltage resistance of the molded body can be compatible. On the other hand, the lower limit of the content of the silicone compound in the composite is not particularly limited, but from the viewpoint of formability and the like, it may be 0.1 parts by mass or more with respect to 100 parts by mass of the epoxy resin. 5 parts by mass or more, may be 7.5 parts by mass or more, or may be 10 parts by mass or more.

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

According to the composition or combination of the metal element-containing powder contained in the composite, it is possible to freely control the electromagnetic characteristics and many other characteristics of the molded body formed by the composite, and the molded body can be used in various industrial products or such Raw materials. The industrial products manufactured using the compound can be, for example, automobiles, medical equipment, electronic equipment, electrical equipment, information communication equipment, home appliances, audio equipment, and general industrial equipment. For example, when the composite contains permanent magnets such as Sm-Fe-N-based alloys or Nd-Fe-B-based alloys as powders containing metal elements, the composites can be used as raw materials for bonded magnets. When the composite contains soft magnetic powders such as Fe-Si-Cr alloys or ferrites as powders containing metal elements, the composites can be used as raw materials for inductors (such as EMI filters) or transformers (such as magnetic core). When the composite contains iron and copper as powders containing metal elements, the formed body (such as a sheet) formed from the composite can be used as an electromagnetic wave shield.

＜Composition of the compound＞ (Resin composition) The resin composition functions as a binding material (binder) for the metal element-containing particles constituting the metal element-containing powder, and imparts mechanical strength to the molded body formed of the composite. For example, when the composite is formed under high pressure using a mold, the resin composition is filled between the particles containing the metal element to bond the particles containing the metal element to each other. By hardening the resin composition in the molded body, the cured product of the resin composition enables the particles containing the metal element to bond to each other more firmly, so that the mechanical strength of the molded body is improved.

The resin composition contains at least an epoxy resin as a thermosetting resin. Since the composite contains an epoxy resin having relatively excellent fluidity among thermosetting resins, the fluidity, storage stability, and moldability of the composite are improved. However, as long as the effect of the present invention is not impaired, the composite may include other resins in addition to epoxy resins. For example, the resin composition may contain at least one of a phenol resin and a polyimide resin as a thermosetting resin. When the resin composition contains both an epoxy resin and a phenol resin, the phenol resin can function as a curing agent for the epoxy resin. The resin composition may also contain a thermoplastic resin. The thermoplastic resin may be, for example, at least one selected from the group consisting of acrylic resin, polyethylene, polypropylene, polystyrene, polyvinyl chloride, and polyethylene terephthalate. The resin composition may include both thermosetting resin and thermoplastic resin. The resin composition may also include silicone resin.

The epoxy resin may be, for example, a resin having two or more epoxy groups in one molecule. The epoxy resin may be, for example, a resin having 3 or more epoxy groups in one molecule. The epoxy resin may also be a multifunctional epoxy resin. The epoxy resin may be, for example, at least one selected from the group consisting of biphenyl type epoxy resin, stilbene type epoxy resin, diphenylmethane type epoxy resin, sulfur atom-containing epoxy resin, and novolac type epoxy resin. Epoxy resin, dicyclopentadiene type epoxy resin, salicylic type epoxy resin, copolymer type epoxy resin of naphthol and phenol, epoxide of aralkyl type phenol resin, bisphenol type epoxy Resin, epoxy resin containing bisphenol skeleton, glycidyl ether epoxy resin of alcohol, glycidyl ether epoxy resin of phenol resin modified by stubble and/or stubble, terpene Glycidyl ether type epoxy resin of modified phenol resin, cyclopentadiene type epoxy resin, glycidyl ether type epoxy resin of polycyclic aromatic ring modified phenol resin, phenol resin containing naphthalene ring Glycidyl ether type epoxy resin, glycidyl ester type epoxy resin, glycidyl type or methyl glycidyl type epoxy resin, alicyclic type epoxy resin, halogenated phenol novolac type ring Oxygen resin, o-cresol novolac type epoxy resin, hydroquinone type epoxy resin, trimethylpropane type epoxy resin, and linear aliphatic epoxy resin obtained by oxidizing olefin bonds with peracetic acid and other peracids.

From the viewpoint of excellent fluidity, the epoxy resin can be selected from biphenyl type epoxy resin, o-cresol novolak type epoxy resin, phenol novolak type epoxy resin, bisphenol type epoxy resin, and bisphenol type epoxy resin. At least one of the epoxy resin of the skeleton, salicylic novolac epoxy resin and naphthol novolac epoxy resin.

The epoxy resin may 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 is excellent in fluidity. The crystalline epoxy resin (epoxy resin with high crystallinity) may be selected from the group consisting of, for example, hydroquinone type epoxy resin, bisphenol type epoxy resin, thioether type epoxy resin, and biphenyl type epoxy resin. At least one of them. Commercially available crystalline epoxy resins can be selected from, for example, 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 (the above are trade names manufactured by 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 (the above are the product names manufactured by Nippon Kayaku Co., Ltd.) , YX-4000, YX-4000H, YL4121H and YX-8800 (the above are the trade names manufactured by Mitsubishi Chemical Corporation) at least one of the group.

From the viewpoint that the molding shrinkage rate of the composite is easily reduced and the heat resistance and voltage resistance of the molded body are easily improved, the resin composition may include a biphenyl aralkyl type epoxy resin and an isocyanate modified epoxy resin At least one of them is an epoxy resin. The resin composition may contain both of the biphenylene aralkyl type epoxy resin and the isocyanate modified epoxy resin as the epoxy resin. The commercially available product of the biphenyl aralkyl type epoxy resin may be NC-3000 manufactured by Nippon Kayaku Co., Ltd., for example. The commercially available product of the isocyanate-modified epoxy resin may be, for example, AER-4001 manufactured by Asahi Kasei Corporation (formerly Asahi Kasei E-Materials Co., Ltd.). From the viewpoint that the heat resistance and withstand voltage of the molded body are easily improved, the resin composition may include a polyfunctional epoxy resin. As a commercially available product of a multifunctional epoxy resin, for example, VG-3101L manufactured by Printec Corporation can be cited.

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

Hardeners are classified into hardeners that harden epoxy resin in the range from low temperature to room temperature, and heat hardening hardeners that harden epoxy resin with heating. The hardener that hardens the epoxy resin in the range from low temperature to room temperature is, for example, aliphatic polyamines, polyaminoamides, and polythiols. The heat-curable hardener is, for example, aromatic polyamines, acid anhydrides, phenol novolac resins, dicyandiamine (DICY), and the like.

When using a hardener that hardens the epoxy resin in the range from low temperature to room temperature, the glass transition point of the hardened epoxy resin is low, and the hardened epoxy resin tends to be soft. As a result, the molded body formed of the composite is also likely to become soft. On the other hand, from the viewpoint of improving the heat resistance of the molded body, the curing agent may preferably be a heat curing type curing agent, more preferably a phenol resin, and still more preferably a phenol novolak resin. In particular, by using a phenol novolak resin as a curing agent, it is easy to obtain a cured product of an epoxy resin with a high glass transition point. As a result, the heat resistance and mechanical strength of the molded body are easily improved.

The phenol resin may be, for example, a copolymerized phenol resin selected from an aralkyl type phenol resin, a dicyclopentadiene type phenol resin, a salicylic phenol resin, a novolak type phenol resin, a benzaldehyde type phenol and an aralkyl type phenol. , Stubble and/or stubble modified phenol resin, melamine modified phenol resin, terpene modified phenol resin, dicyclopentadiene type naphthol resin, cyclopentadiene modified phenol resin, polycyclic aromatic At least one of the group consisting of a cyclic modified phenol resin, a biphenyl type phenol resin, and a triphenylmethane type phenol resin. The phenol resin may also be a copolymer composed of two or more of the above. As a commercially available product of the phenol resin, for example, Tamanol 758 manufactured by Arakawa Chemical Industries, Ltd. or HP-850N manufactured by Hitachi Chemical Co., Ltd. can be used.

The phenol novolak resin may be, for example, a resin obtained by condensing or co-condensing phenols and/or naphthols and aldehydes under an acidic catalyst. The phenols constituting the phenol novolak resin may be selected from the group consisting of phenol, cresol, xylenol, resorcinol, catechol, bisphenol A, bisphenol F, phenylphenol, and aminophenol, for example. At least one of them. The naphthols constituting the phenol novolak resin may be, for example, at least one selected from the group consisting of α-naphthol, β-naphthol, and dihydroxy naphthalene. The aldehydes constituting the phenol novolak resin may be, for example, at least one selected from the group consisting of formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde, and salicaldehyde. As a commercially available product of a phenol novolak resin, HF-3M manufactured by Meiwa Plastic Industries, Ltd., MEW-1800, etc. can be mentioned, for example.

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

The resin composition may contain one of the above-mentioned phenol resins. The resin composition may include a plurality of phenol resins in the above. The resin composition may contain one of the above-mentioned hardeners. The resin composition may contain a plurality of curing agents mentioned above.

The ratio of the active group (phenolic OH group) in the hardener that reacts with the epoxy group in the epoxy resin relative to 1 equivalent of the epoxy group in the epoxy resin may preferably be 0.5 to 1.5 equivalents, more preferably It is 0.6 to 1.4 equivalents, more preferably 0.8 to 1.2 equivalents. When the ratio of active groups in the hardening agent is less than 0.5 equivalent, it is difficult to obtain a sufficient coefficient of elasticity of the obtained hardened product. On the other hand, when the ratio of active groups in the hardening agent exceeds 1.5 equivalents, the mechanical strength of the molded body formed of the composite after hardening tends to decrease. However, even when the ratio of active groups in the hardener is outside the above range, the effects of the present invention can be obtained.

The hardening accelerator (catalyst) is not limited as long as it is a composition that reacts with the epoxy resin to promote the hardening of the epoxy resin, for example. The hardening accelerator may be, for example, imidazoles such as alkyl-substituted imidazole or benzimidazole. The resin composition may be provided with a hardening accelerator. The resin composition may be provided with a plurality of hardening accelerators. When the resin composition contains a hardening accelerator, the moldability and releasability of the composite can be easily improved. In addition, when the resin composition contains a hardening accelerator, the mechanical strength of the molded body (for example, electronic parts) manufactured by using the composite is improved, or the storage stability of the composite under the high temperature/high humidity environment is improved. As a commercially available product of the imidazole-based hardening accelerator, for example, one selected from 2MZ-H, C11Z, C17Z, 1, 2DMZ, 2E4MZ, 2PZ-PW, 2P4MZ, 1B2MZ, 1B2PZ, 2MZ-CN, C11Z-CN, 2E4MZ- At least one of CN, 2PZ-CN, C11Z-CNS, 2P4MHZ, TPZ and SFZ (the above are trade names manufactured by Shikoku Chemicals Corporation). As the hardening accelerator (catalyst), for example, a urea-based catalyst can be used. As a commercially available product of the urea-based catalyst, for example, U-CAT3512T manufactured by San-Apro Ltd. can be cited.

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

The resin composition contains a compound having a siloxane bond (siloxane compound). The siloxane bond system contains two silicon atoms (Si) and one oxygen atom (O) bond, which can be represented by -Si-O-Si-. The compound having a siloxane bond may be a polysiloxane compound. The resin composition may contain one type of silicone compound, or may contain a plurality of types of silicone compound. From the viewpoint that the molding shrinkage rate of the composite is easily reduced and the heat resistance and the voltage resistance of the molded body are easily improved, the resin composition preferably contains the first siloxane compound described later as the siloxane compound. The resin composition may contain only the first siloxane compound as the siloxane compound, or may further contain the second siloxane compound. The resin composition may contain both the first silicone compound and the second silicone compound. The resin composition may contain a silicone compound other than the first silicone compound and the second silicone compound. Hereinafter, the details of the first silicone compound and the second silicone compound will be described.

The first siloxane compound may 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 "structural unit 1".

[Chemical formula 4]

In the above chemical formula (1), n is an integer of 2 to 200, and R ¹ and R ² are each independently an alkyl group having 1 to 10 carbons, an aryl group having 6 to 10 carbons, or an alkoxy group having 1 to 10 carbons. Group, 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 carbons.

^{The plurality of R 1} existing in the first silicone compound may be the same or different from each other. ^{The plurality of R 2} existing in the first silicone compound may be the same as or different from each other. R ¹ and R ² may be the same as or different from each other. The first siloxane compound may have a repeating unit represented by the above chemical formula (1).

From the viewpoint that the molding shrinkage rate of the composite is easily reduced and the heat resistance and voltage resistance of the molded body are easily improved, the first siloxane compound preferably further has a structural unit 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".

[Chemical formula 5]

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

The first siloxane compound may have a plurality of structural units 2. ^{The plurality of R 3} existing in the first silicone compound may be the same as or different from each other. The first siloxane compound may have a repeating unit represented by the above chemical formula (2).

From the viewpoint that the molding shrinkage rate 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) may be referred to as "compound 3".

[Chemical formula 6]

In the above chemical formula (3), n is an integer of 2 to 200. m ₁ and m ₂ 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 carbons, an aryl group having 6 to 10 carbons, an alkoxy group having 1 to 10 carbons, and a monovalent having an epoxy group The organic group, a monovalent organic group having a carboxyl group, or a polyalkylene ether group having 3 to 500 carbons. 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 may include an ether structure. R ¹⁰ and R ¹¹ may each independently be referred to as a divalent hydrocarbon group having 1 to 10 carbon atoms which may contain an oxygen atom or may be bonded via an oxygen atom.

The plural R ⁴ in compound 3 may be the same or different from each other. The plural R ⁵ in compound 3 may be the same or different from each other. R ⁴ , R ⁵ , R ⁶ and R ⁷ may be the same or different from each other. The plural R ⁸ in compound 3 may be the same or different from each other. The plurality of R ⁹ in compound 3 may be the same 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 Compound 3 may be 4000 or more and 20000 or less, for example.

Commercial products of Compound 3 may be, for example, DBL-C31, DBL-C32 manufactured by Gelest, Inc., etc.

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

[Chemical formula 7]

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

R ¹² may be, for example, an alkyl group such as methyl, ethyl, propyl, butyl, isopropyl, isobutyl, tertiary butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, etc.; Vinyl, allyl, butenyl, pentenyl, hexenyl and other alkenyl groups; phenyl, tolyl, xylyl, naphthyl, biphenyl and other aryl groups; benzyl, phenethyl and other aryl groups Alkyl and so on. R ^{12 is} preferably methyl or phenyl.

The second siloxane compound may have a plurality of structural units 4. ^{The plurality of R 12} present in the second silicone compound may be the same or different from each other. The second siloxane compound may have a repeating unit represented by the above chemical formula (4).

[Chemical formula 8]

In the above chemical formula (5), R ¹³ and R ¹⁴ are each independently a monovalent hydrocarbon group having 1 to 12 carbons.

R ¹³ may be, for example, an alkyl group such as methyl, ethyl, propyl, butyl, isopropyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, etc.; Vinyl, allyl, butenyl, pentenyl, hexenyl and other alkenyl groups; phenyl, tolyl, xylyl, naphthyl, biphenyl and other aryl groups; benzyl, phenethyl and other aryl groups Alkyl and so on. R ^{13 is} preferably methyl or phenyl.

R ¹⁴ may be, for example, an alkyl group such as methyl, ethyl, propyl, butyl, isopropyl, isobutyl, tertiary butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, etc.; Vinyl, allyl, butenyl, pentenyl, hexenyl and other alkenyl groups; phenyl, tolyl, xylyl, naphthyl, biphenyl and other aryl groups; benzyl, phenethyl and other aryl groups Alkyl and so on. R ^{14 is} preferably methyl or phenyl.

The second siloxane compound may have a plurality of structural units 5. ^{The plurality of R 13} present in the second silicone compound may be the same as or different from each other. ^{The plurality of R 14} present in the second silicone compound 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 second siloxane compound may have a repeating unit represented by the above chemical formula (5).

From the viewpoint of the storage stability of the second silicone compound, the molecular terminal of the second silicone compound is preferably any one of R ¹² , R ¹³ , R ¹⁴ , a hydroxyl group, and an alkoxy group. The alkoxy group may be, for example, a methoxy group, an ethoxy group, a propoxy group or a butoxy group.

From the viewpoint that the molding shrinkage rate of the composite is easily reduced and the heat resistance and voltage resistance of the molded body are easily improved, the second siloxane compound preferably has 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".

[Chemical formula 9]

In the above chemical formula (6), R ¹⁵ is a monovalent hydrocarbon group having 1 to 12 carbons. R ¹⁶ is a monovalent organic group having an epoxy group.

R ¹⁵ can be, for example, an alkyl group such as methyl, ethyl, propyl, butyl, isopropyl, isobutyl, tertiary butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, etc.; Vinyl, allyl, butenyl, pentenyl, hexenyl and other alkenyl groups; phenyl, tolyl, xylyl, naphthyl, biphenyl and other aryl groups; benzyl, phenethyl and other aryl groups Alkyl and so on. R ^{15 is} preferably methyl or phenyl.

R ¹⁶ can be, for example, 2,3-epoxypropyl, 3,4-epoxybutyl, 4,5-epoxypentyl, 2-glycidoxyethyl, 3-glycidoxypropyl Group, 4-glycidoxybutyl, 2-(3,4-epoxycyclohexyl)ethyl, 3-(3,4-epoxycyclohexyl)propyl, etc. R ^{16 is} preferably 3-glycidoxypropyl.

The second siloxane compound may have a plurality of structural units 6. ^{The plurality of R 15} present in the second silicone compound may be the same as or different from each other. ^{The plurality of R 16} present in the second silicone compound may be the same or different from each other. The second siloxane compound may have a repeating unit represented by the above chemical formula (6).

From the viewpoint that the molding shrinkage rate of the composite is easily reduced and the heat resistance and voltage resistance of the molded body are easily improved, the second silicone compound preferably has a structural unit selected from the following chemical formula (7) A compound with at least one structural unit from the group consisting of the structural unit represented by the following chemical formula (8), the structural unit represented by the following chemical formula (9), and the structural unit represented by the following chemical formula (10). The structural unit represented by the following chemical formula (7) is sometimes referred to as "structural unit 7". The structural unit represented by the following chemical formula (8) may be referred to as "structural unit 8". The structural unit represented by the following chemical formula (9) may be referred to as "structural unit 9". The structural unit represented by the following chemical formula (10) may be referred to as "structural unit 10". A compound having at least one structural unit selected from the group consisting of the aforementioned structural unit 7, structural unit 8, structural unit 9, and structural unit 10 is sometimes referred to as "compound 11". Compound 11 may have all of structural unit 7, structural unit 8, structural unit 9, and structural unit 10.

[Chemical formula 10]

[Chemical formula 11]

上述化學式（9）中，R¹⁸ 為碳數1以上的有機基。[Chemical formula 12]

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

上述化學式（10）中，R¹⁹ 為碳數1以上的有機基。[Chemical formula 13]

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

Compound 11 may have a plurality of structural units 7. Compound 11 may have the repeating unit represented by the above chemical formula (7). Compound 11 may have a plurality of structural units 8. Compound 11 may have the repeating unit represented by the above chemical formula (8). Compound 11 may have a plurality of structural units 9. Compound 11 may have the repeating unit represented by the above chemical formula (9). Compound 11 may have a plurality of structural units 10. Compound 11 may have the repeating unit represented by the above chemical formula (10).

A commercially available product of Compound 11 may be AY42-119 manufactured by Dow Corning Toray Co., Ltd., for example.

The epoxy equivalent of the second silicone compound may be 500 or more and 4000 or less, or 1000 or more and 2500 or less. When the epoxy equivalent is within the above range, the fluidity of the composite is easily improved, and the moldability is easily improved.

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

The weight average molecular weight (Mw) of the second silicone compound may be 1,000 or more and 30,000 or less, preferably 2,000 or more and 20,000 or less, and more preferably 3,000 or more and 10,000 or less. The weight average molecular weight (Mw) can be measured by gel permeation chromatography (GPC), or it can be a value converted using a standard polystyrene calibration curve. The second silicone compound is preferably a random copolymer.

The resin composition may contain one of the above-mentioned silicone compounds, or may contain a plurality of the above-mentioned silicone compounds.

The coupling agent improves the adhesion between the resin composition and the metal element-containing particles constituting the metal element-containing powder, and improves the flexibility and mechanical strength of the molded body formed of the composite. The coupling agent may be, for example, at least one selected from the group consisting of silane-based compounds (silane coupling agents), titanium-based compounds, aluminum compounds (aluminum chelate-based compounds), and aluminum/zirconium-based compounds. The silane coupling agent may be, for example, at least one selected from the group consisting of epoxy silane, mercapto silane, amino silane, alkyl silane, ureido silane, acid anhydride silane, and vinyl silane. In particular, an aminophenyl-based silane coupling agent is preferred. The resin composition may contain one of the above-mentioned coupling agents, or may contain a plurality of the above-mentioned coupling agents.

For the environmental safety, recyclability, molding processability and low cost of the composite, the composite may contain a flame retardant. The flame retardant can be selected from, for example, brominated flame retardants, bulb flame retardants, hydrated metal compound flame retardants, polysiloxane flame retardants, nitrogen-containing compounds, hindered amine compounds, organometallic compounds, and At least one of the group consisting of aromatic engineering plastics. The resin composition may contain one of the above-mentioned flame retardants, or may contain multiple kinds of the above-mentioned flame retardants.

When a mold is used to form a molded body from the composite, the resin composition may contain wax. Wax improves the fluidity of the composite during molding (for example, transfer molding), and acts as a release agent. The wax may be at least any one of fatty acids such as higher fatty acids and fatty acid esters.

The wax may be, for example, at least one selected from the group consisting of fatty acids such as montanic acid, stearic acid, 12-oxystearic acid (12-oxystearic acid), and lauric acid or esters thereof; zinc stearate , Calcium stearate, barium stearate, aluminum stearate, magnesium stearate, calcium laurate, zinc linoleate, calcium ricinoleate, zinc 2-ethylhexanoate and other fatty acid salts; Amine, oleamide, erucamide, behenate, palmitate, laurate, hydroxystearate, methylenebisstearate, ethylenebisstearate Fatty acid amide, ethylene bislaurate amide, distearyl adipamide, ethylene bisoleate amide, dioleyl adipamide, N-stearyl stearyl Fatty acid amides such as amide, N-oleyl stearic acid amide, N-stearyl erucic acid amide, hydroxymethyl stearic acid amide, hydroxymethyl behenic acid amide, etc.; stearic acid Fatty acid esters such as butyl ester; alcohols such as ethylene glycol and stearyl alcohol; polyethers including polyethylene glycol, polypropylene glycol, polytetramethylene glycol and these modified substances; silicone oil, polysilicon Polysiloxane compounds such as oxygen grease; fluorine compounds such as fluorine-based oil, fluorine-based grease, and fluorine-containing resin powder; and paraffin wax, polyethylene wax, amide wax, polypropylene wax, ester wax, carnauba wax ), micro wax and other waxes. For example, as a commercially available product of montanic acid ester, LICOWAX-OP manufactured by Clariant Chemicals Co., Ltd. can be cited. For example, as a commercial product of natural wax, Carnauba wax No. 1 manufactured by CERARICA NODA Co., Ltd. can be cited.

In addition, as a mold release agent, for example, a metal soap formed by bonding a long-chain fatty acid such as montanic acid, stearic acid, 12-hydroxystearic acid, and lauric acid to a metal can be cited. Examples of commercially available metal soaps include Powder Base L manufactured by NOF CORPORATION.

(Powder containing metal elements) The metal element-containing powder (metal element-containing particle) may contain, for example, at least one selected from the group consisting of metal monomers, alloys, and metal compounds. The metal element-containing powder may include, for example, at least one selected from the group consisting of metal monomers, alloys, and metal compounds. The alloy may include at least one selected from the group consisting of solid solution, eutectic, and intermetallic compound. The alloy may be stainless steel (Fe-Cr-based alloy, Fe-Ni-Cr-based alloy, etc.), for example. The metal compound may be an oxide such as ferrite. The metal element-containing powder may contain one metal element or a plurality of metal elements. The metal element contained in the metal element-containing powder may be, for example, a base metal element, a precious metal element, a transition metal element, or a rare earth element. The composite may contain one kind of metal element-containing powder, or it may contain plural kinds of metal element-containing powders with different compositions.

The metal element-containing powder is not limited to the above-mentioned composition. The metal element contained in the metal element-containing powder may be selected from iron (Fe), copper (Cu), titanium (Ti), manganese (Mn), cobalt (Co), nickel (Ni), and zinc (Zn), for example. , Aluminum (Al), tin (Sn), chromium (Cr), barium (Ba), strontium (Sr), lead (Pb), silver (Ag), samarium (Pr), neodymium (Nd), samarium (Sm) And at least one of the group consisting of dysprosium (Dy). The metal element-containing powder may further contain elements other than the metal element. The metal element-containing powder may contain oxygen (О), beryllium (Be), phosphorus (P), boron (B), or silicon (Si), for example. The metal element-containing powder may be a magnetic powder. The metal element-containing powder can be a soft magnetic alloy or a ferromagnetic alloy. The metal element-containing powder may be selected from Fe-Si alloys, Fe-Si-Al alloys (Sendust), Fe-Ni alloys (Permalloy), Fe-Si alloys, and Fe-Si alloys. Cu-Ni series alloy (high-permeability alloy), Fe-Co series alloy (Permendur), Fe-Cr-Si series alloy (electromagnetic stainless steel), Nd-Fe-B series alloy (rare earth magnet) , Sm-Fe-N series alloy (rare-earth magnet), Al-Ni-Co series alloy (aluminium nickel cobalt magnet) and ferrite powder consisting of at least one kind of magnetic powder. Fertilizer iron may be spinel ferrite, hexagonal ferrite, or garnet ferrite, for example. The powder containing metal elements can also be copper alloys such as Cu-Sn series alloys, Cu-Sn-P series alloys, Cu-Ni series alloys or Cu-Be series alloys. The metal element-containing powder may contain one of the above-mentioned elements and the composition, or may contain a plurality of the above-mentioned elements and the composition.

The metal element-containing powder may also be Fe monomer. The powder containing metal elements may also be an alloy containing iron (Fe-based alloy). The Fe-based alloy may be, for example, Fe-Si-Cr-based alloy or Nd-Fe-B-based alloy. The metal element-containing powder may 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 Fe-based alloy, it is easy to produce a molded body with a high space factor and excellent magnetic properties from the composite. The metal element-containing powder may also be an Fe amorphous alloy. As a commercially available product of Fe amorphous alloy powder, for example, AW2-08, KUAMET-6B2, KUAMET 9A4-II (the above are trade names manufactured by Epson Atmix Corporation), DAP MS3, DAP MS7, DAP MSA10, and DAP can be used. PB, DAP PC, DAP MKV49, DAP 410L, DAP 430L, DAP HYB series (above are trade names manufactured by Daido Steel Co., Ltd.), MH45D, MH28D, MH25D and MH20D (above are manufactured by Kobe Steel, Ltd.) At least one of the group consisting of (trade name).

＜Method of manufacturing compound＞ 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 kneaded with a kneader, roll, stirrer, etc. while heating. By heating and mixing the metal element-containing powder and the resin composition, the resin composition adheres to a part or the entire surface of the metal element-containing particles constituting the metal element-containing powder and coats the metal element-containing particles. The resin composition Part or all of the epoxy resin in the product becomes a semi-cured product. As a result, a composite is obtained. It is also possible to obtain a composite by adding wax to the powder obtained by heating and mixing the metal element-containing powder and the resin composition. It is also possible to mix the resin composition and wax in advance.

In the kneading, powders containing metal elements, silicone compounds, epoxy resins, phenol resins and other hardeners, hardening accelerators and coupling agents can be mixed in the tank. It is also possible to put the metal element-containing powder, the siloxane compound, and the coupling agent into the tank for mixing, and then put the epoxy resin, the hardening agent, and the hardening accelerator into the tank to knead the raw materials in the tank. After the silicone compound, epoxy resin, curing agent, and coupling agent are kneaded in the tank, the curing accelerator may be put into the tank, and the raw materials in the tank may be kneaded. It is also possible to make a mixed powder of epoxy resin, hardener and hardening accelerator in advance (resin mixed powder), and then knead the powder containing metal elements, siloxane compound and coupling agent to make metal mixed powder, and then, The metal mixed powder and the above-mentioned resin mixed powder are kneaded.

The kneading time also depends on the type of the kneading machine, the volume of the kneading machine, and the production volume of the compound. For example, it is preferably 1 minute or more, more preferably 2 minutes or more, and still more preferably 3 minutes or more. In addition, the kneading time is preferably 20 minutes or less, more preferably 15 minutes or less, and still more preferably 10 minutes or less. When the kneading time is less than 1 minute, the kneading is insufficient to impair the moldability of the composite, and the degree of hardening of the composite varies. When the kneading time exceeds 20 minutes, for example, the resin composition (for example, epoxy resin and phenol resin) is cured in the tank, and the fluidity and moldability of the composite are easily impaired. When the raw materials in the tank are heated while kneading with a kneader, the heating temperature is, for example, to produce semi-cured epoxy resin (epoxy resin in the B stage) and suppress the hardened epoxy resin (epoxy resin in the C stage). The temperature at which the oxygen resin is generated is sufficient. The heating temperature may also be a temperature lower than the activation temperature of the hardening accelerator. The heating temperature is, for example, preferably 50°C or higher, more preferably 60°C or higher, and still more preferably 70°C or higher. The heating temperature is preferably 150°C or lower, more preferably 120°C or lower, and still more 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 surface of the metal element-containing particles constituting the metal element-containing powder, so that semi-hardened epoxy resin is easily formed, and mixing is easily suppressed. Complete hardening of the epoxy resin in the refining.

＜Molded body＞ The molded body of this embodiment may include the above-mentioned composite. The molded body may include at least one selected from the group consisting of an uncured resin composition, a semi-cured resin composition (B-stage resin composition), and a cured resin composition (C-stage resin composition) . The molded body may also be a hardened product of the above-mentioned composite.

＜Method of manufacturing molded body＞ The method of manufacturing a molded body of this embodiment may include a step of pressurizing the composite in a mold. The manufacturing method of the molded body may only include the step of pressurizing the composite in the mold, or may include other steps in addition to this step. The manufacturing method of the molded body may include the first step, the second step, and the third step. Hereinafter, the details of each step will be described.

In the first step, the above-mentioned method is used to make a composite.

In the second step, a molded body (B-stage molded body) is obtained by pressurizing the composite in a mold. Here, the resin composition is filled between the metal element-containing particles constituting the metal element-containing powder. In addition, the resin composition functions as a bonding material (binder) and binds particles containing metal elements to each other.

As the second step, transfer molding of the composite can also be implemented. In transfer molding, the composite can be pressurized at a pressure of 5 MPa or more and 50 MPa or less. The higher the molding pressure, the easier it is to obtain a molded body with excellent mechanical strength. When considering the mass productivity of the molded body and the life of the mold, the molding pressure is preferably 8 MPa or more and 20 MPa or less. The density of the molded body formed by the transfer molding may preferably be 75% or more and 86% or less, and more preferably 80% or more and 86% or less, relative to the true density of the composite. When the density of the molded body is 75% or more and 86% or less, it is easy to obtain a molded body having excellent mechanical strength. In transfer molding, the second step and the third step can also be performed collectively.

In the third step, the molded body is hardened by heat treatment to obtain a C-stage molded body. Since the composite of this embodiment contains a silicone compound as an elastomer, the overall elasticity of the composite decreases, and the stress acting on the composite decreases as the composite shrinks (thermally hardened). As a result, in the process of forming a molded body by thermal hardening of the composite, the molding shrinkage rate of the composite is reduced. Also, as described above, the mechanism is not clear, but since the composite of this embodiment contains a predetermined amount of a silicone compound as an elastomer, the heat resistance and voltage resistance of the molded body obtained from the composite are obtained. improve. The temperature of the heat treatment may be a temperature at which the resin composition in the molded body is sufficiently hardened. The temperature of the heat treatment may preferably be 100°C or higher and 300°C or lower, more preferably 110°C or higher and 250°C or lower. In order to suppress the oxidation of the metal element-containing powder in the molded body, it is preferable to perform a 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 heat treatment atmosphere. In order to suppress the oxidation of the metal element-containing powder and the deterioration of the cured resin and to fully harden the resin composition, the holding time of the heat treatment temperature may preferably be a few minutes or more and 10 hours or less, more preferably 3 minutes or more and 8 hours or less . [Example]

Hereinafter, the present invention will be described in further detail with examples and comparative examples, but the present invention is not limited by these examples in any way.

(Example 1) [Preparation of the complex] Combine 50 g of biphenyl aralkyl type epoxy resin, 50 g of multifunctional epoxy resin, 14.5 g of phenol novolak resin 1 (hardener), 23.6 g of phenol novolak resin 2 (hardener), 5.9g of urea catalyst (hardening accelerator), 7.5g of zinc laurate type metal soap (release agent), 2.0g of montanate (release agent (wax)) and 4.0g of natural wax (release agent) The mold (wax) is put into a plastic (poly) container. The resin mixture was prepared by mixing the raw materials in a plastic container for 10 minutes. The resin mixture corresponds to all other components in the resin composition except for the silicone compound and the coupling agent. As the biphenylene aralkyl type epoxy resin, NC-3000 manufactured by Nippon Kayaku Co., Ltd. was used. As a multifunctional epoxy resin, VG-3101L manufactured by Printec Corporation was used. As the phenol novolak resin 1, HF-3M manufactured by Meiwa Plastic Industries, Ltd. was used. As the phenol novolak resin 2, MEW-1800 manufactured by Meiwa Plastic Industries, Ltd. was used. As the urea catalyst, U-CAT3512T manufactured by San-Apro Ltd. was used. As zinc laurate type metal soap, Powder Base L manufactured by NOF CORPORATION was used. As the montanic acid ester, LICOWAX-OP manufactured by Clariant Chemicals Co., Ltd. was used. As the natural wax, Carnauba wax No. 1 manufactured by CERARICA NODA Co., Ltd. was used.

The amorphous iron powder 1 and the amorphous iron powder 2 were uniformly mixed for 5 minutes with a pressurized biaxial kneader (manufactured by Nihon Spindle Manufacturing Co., Ltd., volume 5L) to prepare 3741 g of metal element-containing powder. The content of the amorphous iron powder 1 in the metal element-containing powder is 82% by mass. The content of the amorphous iron powder 2 in the metal element-containing powder is 18% by mass. Upgrading 1.9g of methacryloxyoctyltrimethoxysilane (coupling agent), 1.9g of 3-mercaptopropyltrimethoxysilane (coupling agent) and 15g of caprolactone to dimethylpolysiloxane (Compound with siloxane bond) is added to the powder containing metal elements in the biaxial kneader. Then, the contents of the biaxial kneader were heated to 90°C, and the contents of the biaxial kneader were mixed for 10 minutes while maintaining the temperature. Then, the above-mentioned resin mixture was added to the contents of the biaxial kneader, and the contents were melted/kneaded for 15 minutes while maintaining the temperature of the contents at 120°C. After cooling the kneaded material obtained by the above melting/kneading to room temperature, the kneaded material is crushed with a hammer until the kneaded material has a predetermined particle size. In addition, the above-mentioned "melting" refers to the melting of at least a part of the resin composition in the contents of the biaxial kneader. The metal element-containing powder in the composite does not melt during the preparation of the composite. As the amorphous iron powder 1, KUAMET 9A4-II 053C03 (average particle size 24μm) manufactured by Epson Atmix Corporation was used. As the amorphous iron powder 2, AW2-08 (average particle size 5.3μm) manufactured by Epson Atmix Corporation was used. As methacryloxyoctyl trimethoxysilane, KBM-5803 manufactured by Shin-Etsu Chemical Co., Ltd. was used. As 3-mercaptopropyltrimethoxysilane, KBM-803 manufactured by Shin-Etsu Chemical Co., Ltd. was used. As the caprolactone-modified dimethyl polysiloxane, DBL-C32 manufactured by Gelest, Inc. was used. The caprolactone-modified dimethyl polysiloxane is a compound represented by the above chemical formula (3).

The complex of Example 1 was prepared by the above method. The content of the metal element-containing powder in the composite is 95.5% by mass.

(Other Examples and Comparative Examples) Except for changing the formulation of the raw materials as shown in Table 1, in the same manner as in Example 1, composites of other examples and comparative examples were produced. Evaluations related to the complexes of each example were carried out in the same manner as in Example 1. In addition, KBM-403 described in Table 1 is 3-glycidoxypropyltrimethoxysilane manufactured by Shin-Etsu Chemical Co., Ltd.

[Evaluation] The following evaluations were performed using the composites of the respective examples and comparative examples. The results are shown in Table 1.

(Evaluation of heat resistance: 250°C bending test) The composites of the respective examples and comparative examples were subjected to transfer molding under the conditions of a mold temperature of 175°C, a molding pressure of 13.5 MPa, and a curing time of 360 seconds, and then at 175°C. After curing (post cure) for 5.5 hours, a test piece was obtained. The size of the test piece is 80 mm in vertical width × 10 mm in horizontal width × 3.0 mm in thickness. Using an Autograph with a constant temperature bath, a 3-point support type bending test was performed on the test piece. As Autograph, AGS-500A manufactured by Shimadzu Corporation was used. The temperature of the thermostatic bath is 250°C. In the bending test, one surface of the test piece was supported by two fulcrums. A load was applied at the center position between the two fulcrums on the other surface of the test piece. The load when the test piece was broken was measured. The measurement conditions of the bending test are as follows. The distance between the two pivots Lv: 64.0±0.5mm Head speed: 2.0±0.2mm/min Chart speed: 100mm/min Chart full scale: 490N (50kgf) The bending strength σ (unit: MPa) was calculated according to the following formula (A). Calculate the bending elastic coefficient E (unit: GPa) according to the following formula (B). The bending elongation ε (unit: %) was calculated according to the following formula (C). In the following formula, "P" is the load (unit: N) when the test piece is broken. "Lv" is the distance between two pivots (unit: mm). "W" is the horizontal width of the test piece (unit: mm). "T" is the thickness of the test piece (unit: mm). "F/Y" is the slope of the linear part of the load-deflection curve (unit: N/mm). "S" is the deflection of the test piece just before the test piece is broken (unit: mm). σ=(3×P×Lv)/(2×W×t ² ) (A) E=[Lv ³ /(4×W×t ³ )]×(F/Y) (B) ε=(600× s×t)/Lv ² (C)

(Evaluation of withstand voltage: withstand voltage test) The composites of each of the Examples and Comparative Examples were subjected to transfer molding 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, and then post-cured at 175°C for 5.5 hours to produce a thickness of 2.0 mm Test piece. During the withstand voltage test, a stainless steel plate connected to a ground wire, a conductive rubber plate, a test piece, and a stainless steel electrode with a diameter of 10 mm connected to a high-voltage wire are arranged on the insulating board in order. Connect the high-voltage wire and ground wire to the high-voltage output terminal and ground terminal of the high-voltage amplifier, respectively. The waveform output of the function generator is input to a high-voltage amplifier, and a test voltage is generated at a rate of 10V per second from 0V to a maximum of 2000V, and applied to the test piece. The voltage at the point when the current passing through the test piece exceeds 10 mA is read. Next, stainless steel electrodes were placed at different positions on the test piece, and voltage was similarly applied. Repeat a predetermined number of times, and use the average value of the read voltage as the withstand voltage of the test piece (dielectric breakdown voltage: V/mm).

【Table 1】 product name Comparative example 1 Comparative example 2 Comparative example 3 Example 1 Example 2 Example 3 Raw material (g) Epoxy resin NC-3000 50 50 50 50 50 50 VG-3101L 50 50 50 50 50 50 hardener HF-3M 14.5 14.5 14.5 14.5 14.5 14.5 MEW-1800 23.6 23.6 23.6 23.6 23.6 23.6 Hardening accelerator U-CAT3512T 5.9 5.9 5.9 5.9 5.9 5.9 Coupling agent KBM-5803 1.9 1.9 1.5 1.9 1.9 1.5 KBM-803 1.9 1.9 1.0 1.9 1.9 1.0 KBM-403 - - 1.5 - - 1.5 Release agent Powder Base L 7.5 - 7.5 7.5 - 7.5 Licowax-OP 2 2 2 2 2 2 Carnauba wax No.1 4 - 4 4 - 4 Compounds with siloxane bonds DBL-C32 - - - 15 15 15 Powders containing metal elements 3423 3179 3427 3741 3497 3745 Metal magnetic powder filling rate (mass%) 95.5 95.5 95.5 95.5 95.5 95.5 250℃ bending test Elongation(%) 0.79 0.55 0.60 0.74 0.71 0.76 Flexural coefficient of elasticity (GPa) 0.6 1.3 0.6 0.6 1.0 0.9 Flexural strength (MPa) 4.7 5.1 4.8 6.5 6.5 6.7 Withstand voltage test Withstand voltage (V/mm) 90 90 248 352 427 480 [Industrial availability]

The composite of the present invention can obtain a molded body having both heat resistance and voltage resistance, and therefore has high industrial value.

Claims (6)

A composite comprising a powder containing a metal element and a resin composition, the resin composition containing an epoxy resin and a compound having a siloxane bond, and the content of the compound having a siloxane bond relative to the epoxy resin 100 The part by mass is 20 parts by mass or less, and the aforementioned compound having a siloxane bond includes a siloxane compound having a structure represented by the following chemical formula (1), [Chemical formula 1]

In the aforementioned chemical formula (1), n is an integer of 2 to 200, and R ¹ and R ² are each independently an alkyl group having 1 to 10 carbons, an aryl group having 6 to 10 carbons, and an alkoxy group having 1 to 10 carbons. Group, 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 carbons. The compound according to claim 1, wherein the aforementioned siloxane compound further has a structural unit represented by the following chemical formula (2), [chemical formula 2]

In the aforementioned chemical formula (2), R ³ is an alkylene group having 1 to 10 carbon atoms. The compound according to claim 1 or claim 2, which contains the compound represented by the following chemical formula (3) as the aforementioned siloxane compound, [chemical formula 3]

In the aforementioned chemical formula (3), n is an integer of 2 to 200, m ₁ and m ₂ are each independently an integer of 1 to 200, and R ⁴ , R ⁵ , R ⁶ and R ⁷ are each independently a carbon number of 1 to 10 The alkyl group, the aryl group with 6 to 10 carbons, the alkoxy group with 1 to 10 carbons, the monovalent organic group with epoxy group, the monovalent organic group with carboxyl group, or the polycarbonate group with 3 to 500 carbons. In the alkylene ether group, R ⁸ and R ⁹ are each independently an alkylene group having 1 to 10 carbons, and R ¹⁰ and R ¹¹ are each independently a divalent hydrocarbon group having 1 to 10 carbons that may include an ether structure. The composite according to any one of claims 1 to 3, which contains at least one of a biphenyl aralkyl type epoxy resin and an isocyanate modified epoxy resin as the epoxy resin. The compound according to any one of claims 1 to 4, wherein The content of the aforementioned metal element-containing powder is 90% by mass or more and less than 100% by mass. A shaped body comprising the compound according to any one of claims 1 to 5.