TW202219168A - Compound material, molded body, and cured product of compound material - Google Patents

Abstract

A compound material according to one aspect of the present invention comprises a metal powder and a resin composition that contains an epoxy resin, a curing agent and a coupling agent; the coupling agent contains a first silane compound which has a functional group that is selected from among an epoxy group, an amino group, a ureido group and an isocyanate group, and a second silane compound which has a chain hydrocarbon group having 6 or more carbon atoms; and the content of the metal powder is not less than 90% by mass but less than 100% by mass.

Description

Composites, shaped bodies, and cured products of composites

The present invention relates to a composite, a molded body, and a cured product of the composite.

The composite containing the metal powder and the resin composition is used as a raw material of various industrial products according to various physical properties of the metal powder. For example, the composite is used as a raw material for an inductor, a sealing material, an electromagnetic wave shield (EMI shield), or a bonded magnet (see Patent Document 1 below).

[Patent Document 1] Japanese Patent Laid-Open No. 2014-13803

When manufacturing an industrial product from a compound, the compound is supplied and filled into a mold through a flow path, or parts such as a coil are embedded in the compound in the mold. The fluidity of the complex is required in these steps. The fluidity of the composite increases as the content of the metal powder in the composite decreases, but in order to improve the magnetic properties of the composite used in inductors etc., it is desirable that the content (filling ratio) of the metal powder in the composite is high . However, as the content of metal powder in the composite increases, the melt viscosity of the composite increases and the fluidity of the composite decreases. Also, in the step of heating the molded body made of the composite, cracks may be formed in the molded body. Therefore, the composite is required to have excellent fluidity during molding, and to improve the mechanical properties (eg, high-temperature bending properties, etc.) of the molded body at high temperature.

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a composite capable of forming a molded body having excellent fluidity during molding and excellent mechanical properties at high temperatures, a molded body using the same, and a cured product of the composite .

The composite of one aspect of the present invention includes a metal powder and a resin composition containing an epoxy resin, a curing agent and a silane coupling agent, wherein the silane coupling agent includes a first silane compound and a second silane compound, and the first silane compound has an optional The second silane compound has a chain hydrocarbon group having 6 or more carbon atoms from functional groups in an epoxy group, an amine group, a urea group and an isocyanate group, and the content of the metal powder is 90% by mass or more and less than 100% by mass.

A molded body of one aspect of the present invention contains the above-mentioned composite. The cured product of one aspect of the present invention is the cured product of the above-mentioned composite. [Inventive effect]

According to the present invention, it is possible to provide a composite capable of forming a molded body having excellent fluidity during molding and excellent mechanical properties at high temperatures, a molded body using the composite, and a cured product of the composite.

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

[Complex] The composite of this embodiment includes a metal powder and a resin composition. The metal powder may contain, for example, at least one selected from the group consisting of metal monomers, alloys, amorphous powders, and metal compounds. The resin composition contains at least an epoxy resin, a curing agent and a coupling agent. The coupling agent includes a first silane compound and a second silane compound, the first silane compound has a functional group selected from an epoxy group, an amine group, a urea group and an isocyanate group, and the second silane compound has a carbon number of 6 or more. Chain hydrocarbon group. In the composite, metal powder, epoxy resin, curing agent and coupling agent are mixed. The resin composition may further contain a curing accelerator, a mold release agent, an additive, and the like as other components. The resin composition may contain an epoxy resin, a curing agent, a coupling agent, a curing accelerator, a mold release agent, and an additive, and may be the remaining components (nonvolatile components) other than the organic solvent and the metal powder. The additive is a component of the remainder other than the resin, mold release agent, curing agent, curing accelerator, and coupling agent in the resin composition. The additives are, for example, flame retardants, lubricants, and the like. The compound may be a powder (compound powder).

The composite may include metal powder and a resin composition adhered to the surface of each metal particle constituting the metal powder. The resin composition may cover the entire surface of the particle, or may cover only a part of the surface of the particle. The composite may also have an uncured resin composition and metal powder. The composite may include a semi-cured resin composition (for example, a B-stage resin composition) and metal powder. The composite may include both an uncured resin composition and a semi-cured resin composition. The composite can also be formed from a metal powder and a resin composition.

The content of the metal powder in the composite may be 90% by mass or more and less than 100% by mass relative to the mass of the entire composite. When the content of the metal powder increases, it becomes difficult to secure the releasability of the molded body, and the workability tends to deteriorate. From the viewpoint of the magnetic properties of the molded body, the content of the metal powder is preferably 92 mass % or more, more preferably 94 mass % or more, further preferably 95 mass % or more, and particularly preferably 96 mass % or more. The upper limit of the content of the metal powder may be 99 mass % or less, 98 mass % or less, or 97.5 mass % or less.

(resin composition) The resin composition functions as a binding material (binder) for the metal particles constituting the metal powder, and imparts mechanical strength to the molded body formed of the composite. For example, when the composite is shaped under high pressure using a mold, the resin composition contained in the composite is filled between the metal particles to bond the particles to each other. By curing the resin composition in the molded body, the cured product of the resin composition binds the metal particles to each other more firmly, thereby improving the mechanical strength of the molded body.

The resin composition of this embodiment can improve the fluidity of a composite by containing an epoxy resin as a thermosetting resin. The epoxy resin may be, for example, a resin having two or more epoxy groups in one molecule. The kind of epoxy resin is not particularly limited, and can be selected according to the desired properties of the composition and the like.

Examples of epoxy resins include the following: biphenyl-type epoxy resins, stilbene-type epoxy resins, diphenylmethane-type epoxy resins, sulfur atom-containing epoxy resins, novolak-type epoxy resins, bicyclic epoxy resins Pentadiene-type epoxy resins, salicylic epoxy resins, copolymerized epoxy resins of naphthols and phenols, epoxides of aralkyl-type phenolic resins, bisphenol-type epoxy resins, containing bisphenol skeleton Epoxy resins, glycidyl ether epoxy resins of alcohols, glycidyl ether epoxy resins of stubble and/or stubble-modified phenolic resins, and terpene-modified phenolic resins Oxypropyl ether type epoxy resin, cyclopentadiene type epoxy resin, glycidyl ether type epoxy resin of polycyclic aromatic ring modified phenolic resin, glycidyl ether type of phenolic resin containing naphthalene ring Epoxy resin, glycidyl ester type epoxy resin, glycidyl type or methylglycidyl type epoxy resin, alicyclic type epoxy resin, halogenated phenol novolac type epoxy resin, o-cresol Novolak-type epoxy resin, hydroquinone-type epoxy resin, trimethylolpropane-type epoxy resin, and linear aliphatic epoxy resin obtained by oxidizing olefin bond with peracid such as peracetic acid.

From the viewpoint of fluidity, the epoxy resin may contain a type selected from the group consisting of biphenyl type epoxy resin, o-cresol novolak type epoxy resin, phenol novolak type epoxy resin, bisphenol type epoxy resin, having a bisphenol skeleton At least one selected from the group consisting of epoxy resin, salical novolac type epoxy resin and naphthol novolac type epoxy resin.

From the viewpoint of mechanical strength, the epoxy resin may contain at least one selected from the group consisting of a biphenylene aralkyl type epoxy resin and an o-cresol novolak type 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 (highly crystalline epoxy resin) may contain, for example, a hydroquinone-type epoxy resin, a bisphenol-type epoxy resin, a sulfide-type epoxy resin, and a biphenyl-type epoxy resin selected from the group consisting of at least one of them.

Examples of commercially available crystalline epoxy resins include 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 and BREN-10S (the above are trade names manufactured by Nippon Kayaku Co., Ltd. ); YX-4000, YX-4000H, YL4121H and YX-8800 (the above are trade names manufactured by Mitsubishi Chemical Corporation).

The resin composition may contain one of the above epoxy resins. The resin composition may contain plural types of epoxy resins described above. Among the above epoxy resins, the resin composition may contain an epoxy resin containing a biphenyl skeleton, an o-cresol novolac epoxy resin, or a polyfunctional epoxy resin containing two or more epoxy groups.

The curing agent is classified into a curing agent that cures epoxy resins in a range from a low temperature to room temperature, and a curing agent of a heat curing type that cures epoxy resins with heating. Examples of curing agents for curing epoxy resins in the range from low temperature to room temperature are aliphatic polyamines, polyamidoamines, and polythiols. The heat-curable curing agent is, for example, aromatic polyamines, acid anhydrides, phenol novolac resins, dicyandiamine (DICY), and the like. The kind of the curing agent is not particularly limited, and can be selected according to the desired properties of the composition and the like.

When a curing agent that cures epoxy resins in the range from low temperature to room temperature is used, the glass transition point of the cured epoxy resin is low, and the cured epoxy resin tends to be soft. As a result, the molded body formed of the composite tends 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-curable 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, a cured product of an epoxy resin having a high glass transition point can be easily obtained. As a result, the heat resistance and mechanical strength of the molded body are easily improved.

The phenolic resin may contain, for example, a copolymerization-type phenolic resin selected from aralkyl-type phenolic resins, dicyclopentadiene-type phenolic resins, salicylic-type phenolic resins, novolak-type phenolic resins, benzaldehyde-type phenols, and aralkyl-type phenols , stubble and/or stubble-modified phenolic resin, melamine-modified phenolic resin, terpene-modified phenolic resin, dicyclopentadiene-type naphthol resin, cyclopentadiene-modified phenolic resin, polycyclic aromatic At least one of the group consisting of ring-modified phenolic resin, biphenyl-type phenolic resin and triphenylmethane-type phenolic resin. The phenolic resin may be a copolymer composed of two or more of the above. As a commercial item of a phenol resin, for example, Tamanol 758 manufactured by Arakawa Chemical Industries, Ltd. or HP-850N manufactured by Hitachi Chemical Co., Ltd., etc. 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 novolac resin may contain, for example, a group selected from the group consisting of phenol, cresol, xylenol, resorcinol, catechol, bisphenol A, bisphenol F, phenylphenol and aminophenol at least one of them. The naphthols constituting the phenol novolak resin may contain, for example, at least one selected from the group consisting of α-naphthol, β-naphthol, and dihydroxynaphthalene. The aldehydes constituting the phenol novolak resin may contain, for example, at least one selected from the group consisting of formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde, and salivarial.

The curing agent may be, for example, a compound having two phenolic hydroxyl groups in one molecule. The compound having two phenolic hydroxyl groups in one molecule may contain, 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 plural types of phenol resins described above. The resin composition may contain one of the above-mentioned curing agents. The resin composition may contain plural kinds of curing agents described above.

The ratio of the active group (phenolic OH group) in the curing agent that reacts with the epoxy group in the epoxy resin may be preferably 0.5 to 1.5 equivalents, more preferably 1 equivalent of the epoxy group in the epoxy resin. 0.6 to 1.4 equivalents, more preferably 0.7 to 1.2 equivalents. When the ratio of active groups in the curing agent is less than 0.5 equivalent, it is difficult to obtain a 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, the mechanical strength after curing of the molded body formed of the composite tends to decrease. However, even when the ratio of the active group in the curing agent is outside the above-mentioned range, the effect of the present invention can be obtained.

The coupling agent can improve the adhesiveness between the resin composition and the metal element-containing particles constituting the metal powder, thereby improving the flexibility and mechanical strength of the molded body formed of the composite. The resin composition of the present embodiment can improve the fluidity and curing characteristics of the composite by containing a specific silane compound as a coupling agent. The coupling agent includes a first silane compound and a second silane compound, the first silane compound has a functional group selected from an epoxy group, an amine group, a urea group and an isocyanate group, and the second silane compound has a carbon number of 6 or more. Chain hydrocarbon group. In the present specification, a chain hydrocarbon group having 6 or more carbon atoms may be referred to as a long-chain hydrocarbon group.

By including the first silane compound in the resin composition, a molded body having excellent high-temperature bending properties can be formed. The functional group which the first silane compound has can react with an epoxy resin or a curing agent. The first silane compound is a silane compound that does not have a long-chain hydrocarbon group.

Examples of the first silane compound having an epoxy group include 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriethyl Oxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltrimethoxysilane Silane and 3-glycidoxypropyltriethoxysilane.

Examples of the first silane compound having an amino group include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-2-(aminoethyl)-3- Aminopropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropyltriethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyl Dimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldiethoxysilane, N-phenyl-3-aminopropylmethyldimethoxysilane , N-phenyl-3-aminopropylmethyldiethoxysilane and N-phenyl-3-aminopropyltrimethoxysilane.

Examples of the first silane compound having a ureido group include 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, and 3-ureidopropylmethyldimethoxysilane. and 3-ureidopropylmethyldiethoxysilane.

Examples of the first silane compound having an isocyanate group include 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-isocyanatopropylmethyldimethoxysilane, and 3-isocyanatopropylmethyldimethoxysilane. Isocyanate propyl methyl diethoxy silane.

From the viewpoint of further improving high-temperature bending properties, the content of the first silane compound may be 0.5 parts by mass or more and 10 parts by mass or less, 1.0 parts by mass or more and 8.0 parts by mass or less, or 2.0 parts by mass relative to 100 parts by mass of the epoxy resin. part or more and 7.0 parts by mass or less.

By including the second silane compound in the resin composition, the fluidity at the time of molding the composite can be improved. The carbon number of the chain hydrocarbon group which the second silane compound has is 6 or more, may be 7 or more or 8 or more, and may be 20 or less, 16 or less, or 14 or less. The second silane compound may have a styryl group, a (meth)acryloyl group, or a vinyl group.

Examples of the second silane compound include hexyltrimethoxysilane, hexyltriethoxysilane, heptyltrimethoxysilane, heptyltriethoxysilane, octyltrimethoxysilane, and octyltriethoxysilane. Silane, dodecyltrimethoxysilane, dodecyltriethoxysilane, acryloxyhexyltrimethoxysilane, acryloxyhexyltriethoxysilane, methacryloyloxyhexyl Trimethoxysilane, methacryloyloxyhexyltriethoxysilane, acryloyloxyheptyltrimethoxysilane, acryloyloxyheptyltriethoxysilane, methacryloyloxyheptyltrimethy Oxysilane, methacrylooxyheptyltriethoxysilane, acrylooxyoctyltrimethoxysilane, acrylooxyoctyltriethoxysilane, methacrylooxyoctyltrimethyl Oxysilane and Methacrylooxyoctyltriethoxysilane.

From the viewpoint of further improving fluidity, the content of the second silane compound may be 0.1 parts by mass or more and 5.0 parts by mass or less, 0.5 parts by mass or more and 4.0 parts by mass or less, or 1.0 parts by mass relative to 100 parts by mass of the epoxy resin more than 3.0 parts by mass or less.

The coupling agent may further contain a third silane compound having a mercapto group. The third silane compound is a silane compound that does not have a long-chain hydrocarbon group. Examples of the third silane compound include 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, and 3-mercaptopropylmethylsilane. Diethoxysilane.

From the viewpoint of achieving both fluidity and mechanical properties, the content of the coupling agent may be 1.0 parts by mass or more and 20 parts by mass or less, 2.0 parts by mass or more and 15 parts by mass or less, or 3.0 parts by mass relative to 100 parts by mass of the epoxy resin more than 10 parts by mass or less.

The curing accelerator is not limited, for example, as long as it reacts with the epoxy resin and accelerates the curing of the epoxy resin. The curing accelerator may be, for example, a phosphorus-based curing accelerator, an imidazole-based curing accelerator, or a urea-based curing accelerator. By containing the curing accelerator in the resin composition, the moldability and releasability of the composite can be improved. In addition, when the resin composition contains a curing accelerator, the mechanical strength of a molded body (eg, electronic component) produced using the composite is improved, or the storage stability of the composite in a high temperature/high humidity environment is improved.

Examples of the phosphorus-based curing accelerator include phosphine compounds and phosphonium salt compounds.

As a commercially available imidazole-based curing accelerator, for example, a product selected from the group consisting of 2MZ-H, C11Z, C17Z, 1,2DMZ, 2E4MZ, 2PZ-PW, 2P4MZ, 1B2MZ, 1B2PZ, 2MZ-CN, C11Z-CN, 2E4MZ- At least one of the group consisting of CN, 2PZ-CN, C11Z-CNS, 2P4MHZ, TPZ and SFZ (the above are trade names manufactured by Shikoku Chemicals Corporation).

The urea-based curing accelerator is not particularly limited as long as it is a curing accelerator having a urea group, but an alkyl urea-based curing accelerator having an alkyl urea group is preferred from the viewpoint of improving storage stability. good. As an alkylurea type hardening accelerator which has an alkylurea group, an aromatic alkylurea and an aliphatic alkylurea are mentioned, for example. Examples of commercially available alkylurea-based curing accelerators include U-CAT3512T (trade name, manufactured by San-Apro Ltd., aromatic dimethylurea) and U-CAT3513N (trade name, manufactured by San-Apro Ltd.) . manufacture, aliphatic dimethyl urea). Among these, the aromatic alkyl urea is preferable because the cracking temperature is appropriately low, and the complex is easily cured efficiently.

The compounding quantity of a hardening accelerator will not be specifically limited if it is an amount which can obtain a hardening-accelerating effect. From the viewpoint of improving the curability and fluidity of the resin composition during moisture absorption, the amount of the curing accelerator to be blended may preferably be 0.1 parts by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the epoxy resin, and more Preferably it is 0.5 mass part or more and 15 mass parts or less, More preferably, it is 1.0 mass part or more and 10 mass parts or less. When the compounding amount of the curing accelerator is 0.1 part by mass or more, a sufficient curing acceleration effect can be easily obtained. When the compounding quantity of a hardening accelerator is 30 mass parts or less, the storage stability of a composite is hard to fall. 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 phenolic resin. However, even when the compounding amount and content of the curing accelerator are outside the above-mentioned ranges, the effects of the present invention can be obtained.

The resin composition may contain a compound having a siloxane bond (siloxane compound) as an additive, because the molding shrinkage rate of the composite is easily reduced, and the heat resistance and withstand voltage of the molded body are easily improved. The siloxane bond is a bond consisting of 2 silicon atoms (Si) and 1 oxygen atom (O), which can be represented by -Si-O-Si-. The compound having a siloxane bond may be a polysiloxane compound.

The content of the siloxane compound may be 1 part by mass or more and 50 parts by mass or less, 5 parts by mass or more and 45 parts by mass or less, or 10 parts by mass or more and 40 parts by mass or less with respect to 100 parts by mass of the epoxy resin.

The composite may contain a flame retardant for environmental safety, recyclability, formability, and low cost of the composite. The flame retardant can be selected from, for example, bromine-based flame retardants, phosphorus-based flame retardants, hydrated metal compound-based flame retardants, silicone-based flame retardants, nitrogen-containing compounds, hindered amine compounds, organometallic compounds, and aromatic compounds. At least one of the group consisting of plastics. The resin composition may contain one of the above-mentioned flame retardants, or may contain plural kinds of the above-mentioned flame retardants.

When a molded body is formed from the composite using a mold, the resin composition may contain wax. Waxes improve the fluidity of the composite during molding (eg, transfer casting) and function as a mold release agent. The wax may be at least any one of fatty acids such as higher fatty acids and fatty acid esters.

For example, the wax may be at least one selected from the group consisting of: montanic acid, stearic acid, 12-oxystearic acid, lauric acid and other fatty acids or esters thereof; zinc stearate, Calcium stearate, barium stearate, aluminum stearate, magnesium stearate, calcium laurate, zinc laurate, zinc linoleate, calcium ricinoleate, zinc 2-ethylhexanoate and other fatty acid salts; hard amide oleate, amide oleate, amide erucate, amide behenate, amide palmitate, amide laurate, amide hydroxystearate, amide bis-stearate, ethylene glycol diamide bis-stearate, diamide ethyl dilaurate, diamide distearyl adipate, diamide dioleate dioleate, dioleyl diamide dioleate, N-stearyl Fatty acid amides such as base stearic acid amide, N-oleyl stearic acid amide, N-stearyl erucic acid amide, hydroxymethyl stearic acid amide, hydroxymethyl behenic acid amide; Fatty acid esters such as butyl stearate; alcohols such as ethylene glycol and stearyl alcohol; polyethers including polyethylene glycol, polypropylene glycol, polytetramethylene glycol and their modifications; silicone oil, Silicone grease and other polysiloxanes; fluorine-based oil, fluorine-based grease, fluorine-containing resin powder and other fluorine compounds; and paraffin wax, polyethylene wax, amide wax, polypropylene wax, ester wax, carnauba wax (Carnauba wax) wax), Micro wax (Micro wax) and other waxes.

From the viewpoint of both fluidity and releasability, the wax content may be 1 part by mass or more and 20 parts by mass or less, 2 parts by mass or more and 15 parts by mass or less, or 3 parts by mass relative to 100 parts by mass of the epoxy resin more than 10 parts by mass or less.

(metal powder) The metal powder (particles containing a metal element) may contain, for example, at least one selected from the group consisting of a single metal, an alloy, and a metal compound. The metal element-containing powder may contain, for example, at least one selected from the group consisting of metal monomers, alloys, and metal compounds. The alloy may contain at least one selected from the group consisting of solid solution, eutectic, and intermetallic. The alloy may be, for example, stainless steel (Fe-Cr-based alloy, Fe-Ni-Cr-based alloy, or the like). The metal compound may be, for example, an oxide such as ferric iron. The metal powder may contain one metal element or a plurality of metal elements. The metal element contained in the metal powder may be, for example, a base metal element, a noble metal element, a transition metal element or a rare earth element. The composite may contain one metal-containing element powder, or may contain a plurality of metal-containing element powders with different compositions.

The metal element contained in the metal powder can be selected from iron (Fe), copper (Cu), titanium (Ti), manganese (Mn), cobalt (Co), nickel (Ni), zinc (Zn), aluminum ( Al), tin (Sn), chromium (Cr), niobium (Nb), barium (Ba), strontium (Sr), lead (Pb), silver (Ag), strontium (Pr), neodymium (Nd), samarium ( At least one of the group consisting of Sm) and dysprosium (Dy). From the viewpoint of improving the magnetic properties, it is preferable that the metal powder contains at least one metal element selected from the group consisting of iron, cobalt, and nickel. The metal powder may further contain elements other than metal elements. The metal powder may contain, for example, carbon (C), oxygen (О), beryllium (Be), phosphorus (P), sulfur (S), boron (B) or silicon (Si).

The metal powder may be magnetic powder. The metal powder can also be a soft magnetic alloy or a ferromagnetic alloy. For example, the metal powder may be selected from Fe-Si-based alloys, Fe-Si-Al-based alloys (Sendust), Fe-Ni-based alloys (Permalloy), Fe-Cu-Ni series alloy (high magnetic permeability alloy), Fe-Co series alloy (iron cobalt alloy (Permendur)), Fe-Cr-Si series alloy (electromagnetic stainless steel), Nd-Fe-B series alloy (rare earth magnet), Sm- Magnetic powder of at least one of the group consisting of Fe-N-based alloys (rare earth magnets), Al-Ni-Co-based alloys (Alnico magnets) and ferrite. The ferric iron can be, for example, spinel ferrite, hexagonal ferrite or garnet ferrite. The metal powder may 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 powder may contain one of the above-described elements and compositions, or may contain plural kinds of the above-described elements and compositions.

The metal powder can also be Fe monomer. The metal powder may be an alloy containing iron (Fe-based alloy). The Fe-based alloy may be, for example, a Fe-Si-Cr-based alloy or a Nd-Fe-B-based alloy. The metal element-containing powder may be at least any one of amorphous iron powder and carbonyl iron powder. When the metal powder contains at least one of Fe alone and Fe-based alloys, it is easy to produce a molded body having a high space factor and excellent magnetic properties from the composite. The metal powder can also be Fe amorphous alloy.

As a commercial item of Fe amorphous alloy powder, for example, AW2-08, KUAMET-6B2 (the above are 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 (the above are the trade names manufactured by Daido Steel Co., Ltd.), MH45D, MH28D, MH25D and MH20D (the above are the trade names manufactured by Kobe Steel, Ltd.) at least one of the group.

<Production method of composite> In the production of the composite, the metal powder and the resin composition (each component constituting the resin composition) are mixed while being heated. For example, the metal powder and the resin composition are kneaded with a kneader, a roll, a mixer, or the like while being heated. By heating and mixing the metal powder and the resin composition, the resin composition adheres to a part or the whole of the surface of the metal element-containing particles constituting the metal powder and covers the metal element-containing particles, so that the epoxy resin in the resin composition Part or all of the resin becomes a semi-cured product. As a result, a complex is obtained. A compound can also be obtained by further adding wax to the powder obtained by heating and mixing the metal powder and the resin composition. The resin composition and wax may also be mixed in advance.

During the kneading, the metal powder, epoxy resin, curing agent, curing accelerator and coupling agent may be kneaded in a tank. After the metal powder and the coupling agent are put into the tank and mixed, the epoxy resin, the curing agent, and the curing accelerator may be put into the tank, and the raw materials in the tank may be kneaded. After kneading the siloxane compound, epoxy resin, curing agent, and coupling agent in the tank, the curing accelerator may be put into the tank, and the raw materials in the tank may be kneaded. Mixed powder (resin mixed powder) of epoxy resin, curing agent, and curing accelerator may be prepared in advance, and then the metal powder and the coupling agent may be kneaded to produce metal mixed powder, and then the metal mixed powder and the above-mentioned resin may be mixed. Powder is mixed.

The kneading time also depends on the type of 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 even more preferably 3 minutes or more. Further, the kneading time is preferably 20 minutes or less, more preferably 15 minutes or less, and even more 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 varies. When the kneading time exceeds 20 minutes, for example, curing of the resin composition (eg, epoxy resin and phenolic resin) proceeds in a tank, and the fluidity and formability of the composite are likely to be impaired.

When the raw materials in the tank are heated and kneaded with a kneader, the heating temperature is such that, for example, a semi-cured epoxy resin (B-stage epoxy resin) is formed and the cured epoxy resin (C-stage epoxy resin) is suppressed. Oxygen resin) can be generated at the temperature. The heating temperature may be lower than the activation temperature of the curing accelerator. The heating temperature is, for example, preferably 50°C or higher, more preferably 60°C or higher, and even more preferably 70°C or higher. The heating temperature is preferably 150°C or lower, more preferably 120°C or lower, and even more preferably 110°C or lower. When the heating temperature is within the above range, the resin composition in the tank is softened to easily coat the surface of the metal element-containing particles constituting the metal powder, so that a semi-cured epoxy resin is easily formed, and it is easy to suppress the Complete curing of epoxy resin.

[molded body] The molded body of the present embodiment may include the above-mentioned composite. The molded body of the present embodiment may include a cured product of the above-mentioned composite. The molded body may contain 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 of the present embodiment can be used as a sealing material for electronic parts or electronic circuit boards. According to the present embodiment, cracks in the molded body caused by the difference in thermal expansion coefficient between the metal member and the molded body (sealing material) included in the electronic component or the electronic circuit board can be suppressed.

The cured product of the composite is a cured product of the metal powder and the resin composition, and the content of the metal powder is 90% by mass or more and less than 100% by mass. From the viewpoint of improving the strength of the cured product, the flexural strength of the cured product at 250° C. is preferably 7.0 MPa or more, more preferably 8.0 MPa or more, and even more preferably 8.5 MPa or more. The upper limit of the bending strength is about 10 MPa. From the viewpoint of imparting flexibility to the cured product, the flexural modulus of elasticity at 250° C. of the cured product may be 1.3 GPa or less, 1.2 GPa or less, or 1.1 GPa or less. The lower limit of the bending elastic coefficient is about 0.1 GPa. The value obtained by dividing the flexural strength (MPa) at 250°C by the flexural modulus of elasticity (GPa) at 250°C can be used as the reliability index of the cured product. The index is preferably 9.0×10 ^-3 or higher, more preferably 9.2×10 ^-3 or higher, and even more preferably 10.4×10 ^-3 or higher. The upper limit of this index is not particularly limited, and may be, for example, 5×10 ⁻² or less.

<Manufacturing method of molded body> The manufacturing method of the molded object of this embodiment may include the process of pressurizing a compound in a mold. The manufacturing method of a molded object may include the process of pressurizing the composite covering a part or the whole of the surface of a metal member in a metal mold|die. The method for producing a molded body may include only the step of pressurizing the composite in a mold, or may include other steps in addition to this step. The manufacturing method of a molded object may include a 1st process, a 2nd process, and a 3rd process. Hereinafter, the details of each step will be described.

In the first step, the composite is produced using the method described above.

In the second step, a shaped body (B-stage shaped body) is obtained by pressurizing the composite in a mold. In the second step, a formed body (a B-stage formed body) can be obtained by pressurizing the composite covering a part or the whole of the surface of the metal member in a mold. In the second step, the resin composition is filled between the respective metal-element-containing particles constituting the metal-element-containing powder. Furthermore, the resin composition functions as a binding material (binder), and binds the particles containing the metal element to each other.

As a second step, transfer molding of the composite can also be performed. In transfer casting, the composite may 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 the mass productivity of the molded body and the life of the mold are considered, the molding pressure is preferably 8 MPa or more and 20 MPa or less. The density of the molded body formed by transfer molding may be preferably 75% or more and 86% or less, more preferably 80% or more and 86% or less, with respect 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 excellent in mechanical strength. In the transfer injection molding, the second step and the third step may be performed collectively.

In the third step, the formed body is cured by heat treatment to obtain a C-stage formed body. The temperature of the heat treatment may be a temperature at which the resin composition in the molded body is sufficiently cured. The temperature of the heat treatment may 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 the oxidation of the metal powder in the compact, it is preferable to perform the heat treatment in an inert atmosphere. When the heat treatment temperature exceeds 300° C., the metal powder is oxidized or the resin cured product is deteriorated due to a trace amount of oxygen inevitably contained in the atmosphere of the heat treatment. In order to suppress oxidation of the metal powder and deterioration of the cured resin product and sufficiently cure the resin composition, the holding time of the heat treatment temperature may be preferably several 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 reference to Examples and Comparative Examples, but the present invention is not limited to these examples at all.

The details of each component used in the preparation of the composites of Examples and Comparative Examples are shown below.

(epoxy resin) Biphenylene aralkyl type epoxy resin (trade name: NC-3000 manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent: 275 g/eq) Polyfunctional epoxy resin (trade name: TECHMORE VG3101L, manufactured by Printec Corporation, epoxy equivalent: 215 g/eq)

(Hardener) Triphenylmethane type phenolic resin (trade name: HE910-09 manufactured by AIR WATER INC., hydroxyl equivalent: 101 g/eq) Biphenylene aralkyl type phenolic resin (trade name: MEHC-7841-4S manufactured by Meiwa Plastic Industries, Ltd., hydroxyl equivalent weight: 166 g/eq)

(coupling agent) 3-Glycidoxypropyltrimethoxysilane (trade name: KBM-403 manufactured by Shin-Etsu Chemical Co., Ltd.) 3-Mercaptopropyltrimethoxysilane (trade name: KBM-803 manufactured by Shin-Etsu Chemical Co., Ltd.) Methacryloyloxyoctyltrimethoxysilane (trade name: KBM-5803 manufactured by Shin-Etsu Chemical Co., Ltd.)

(curing accelerator) Imidazole-based curing accelerator (trade name: 2P4MHZ-PW manufactured by Shikoku Chemicals Corporation) (release agent) Zinc laurate (trade name: Powder Base L manufactured by NOF CORPORATION) Partially saponified montanate wax (trade name: Licowax-OP, manufactured by Clariant Chemicals Co., Ltd.) (additive) Caprolactone-modified dimethyl silicone (trade name: DBL-C32 manufactured by Gelest, Inc.)

(metal powder) Amorphous iron powder (trade name: 9A4-II manufactured by Epson Atmix Corporation, average particle size 24 μm) Amorphous iron powder (trade name: AW2-08 manufactured by Epson Atmix Corporation, average particle size 5.3 μm)

[Preparation of the complex] (Examples 1 to 5) The epoxy resin, curing agent, curing accelerator, and mold release agent shown in Table 1 were put into a plastic container in the amount (unit: g) shown in the table. A resin mixture was prepared by mixing the materials in a plastic container for 10 minutes. The resin mixture corresponds to all other components in the resin composition except the coupling agent and additives.

Two types of amorphous iron powders shown in Table 1 were uniformly mixed for 5 minutes in a pressurized biaxial kneader (manufactured by Nihon Spindle Manufacturing Co., Ltd., capacity 5 L) to prepare metal powders. The coupling agents and additives shown in Table 1 were added to the metal powder in the biaxial kneader. Next, 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. Next, 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 pulverized with a hammer until the kneaded material has a predetermined particle size. In addition, the above-mentioned "melting" means melting of at least a part of the resin composition in the contents of the biaxial kneader. The metal powder in the composite does not melt during the preparation of the composite. The composites of Examples 1 to 5 were prepared by the above method.

(Comparative Examples 1 to 3) The composites of Comparative Examples 1 to 3 were prepared in the same manner as in the Examples, except that the types and compounding amounts of the respective components were changed as shown in Table 2.

[Evaluation of the complex] The following evaluations were performed on the composites obtained in Examples and Comparative Examples. The results are shown in Tables 1 and 2.

(fluidity) The evaluation of fluidity was performed using a flow tester (Flow tester) CFT-100 manufactured by Shimadzu Corporation. The compound 7g was molded to produce a tablet. The evaluation of fluidity was implemented using the tablet under the conditions of 130° C., residual heat of 20 seconds, and a load of 100 kg. The indentation distance (unit: mm) of the plunger until the compound stopped flowing was taken as the stroke of the flow tester (Stroke), and the time until the compound stopped flowing was measured as the flow time, which was used as an index of fluidity.

(gel time) The gel time of the complex was measured using the following method. Using a Curemeter (manufactured by JSR Trading Co., Ltd.), the gelation time was measured under the conditions of a sample amount of 1.5 mL and 140°C. The start time of the torque rise in the obtained graph was taken as the gelation time. The shorter the gel time, the higher the curability.

(Bending test) After the composite was transfer-molded under the conditions of a molding die temperature of 140° C., a molding pressure of 13.5 MPa, and a curing time of 360 seconds, a test piece was obtained by post-curing at 180° C. for 2 hours. The dimensions of the test piece were 80 mm in length and 10 mm in width and 3.0 mm in thickness.

The test piece was subjected to a three-point support type bending test at 250° C. using an autostereograph with a constant temperature bath. As an autostereographer, AGS-500A manufactured by Shimadzu Corporation was used. In the bending test, one surface of the test piece was supported by two fulcrums. A load was applied to the center 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. Distance Lv between 2 fulcrums: 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 from the following formula (A). The bending elastic modulus E (unit: GPa) was calculated according to the following formula (B). In the following formula, "P" is the load (unit: N) when the test piece is broken. "Lv" is the distance (unit: mm) between the two fulcrums. "W" is the lateral width (unit: mm) of the test piece. "t" is the thickness (unit: mm) of the test piece. "F/Y" is the slope (unit: N/mm) of the straight portion of the load-deflection curve. σ=(3×P×Lv)/(2×W×t ² ) (A) E=[Lv ³ /(4×W×t ³ )]×(F/Y) (B)

(reliability) The value obtained by dividing the flexural strength (MGa) at 250°C by the flexural modulus of elasticity (GPa) at 250°C was used as an evaluation index of reliability. The larger the value, the better the balance between strength and elastic modulus.

(reflow treatment) By transfer molding, a copper metal member was sealed with the composite, and the composite was cured to obtain a molded body. The formed body was subjected to reflow treatment. The maximum heating temperature in the reflow treatment was 260°C. The heating time was 300 seconds. After the reflow treatment, the molded body was observed, and the presence or absence of cracks in the molded body was investigated. "A" in the table indicates that no cracks were formed in the molded body, and "B" indicates that cracks were formed in the molded body.

【Table 1】 Example 1 2 3 4 5 epoxy resin NC-3000 50 50 50 50 50 VG-3101L 50 50 50 50 50 Hardener HE910-09 twenty two twenty two twenty two twenty two twenty two MEHC-7841-4S 29 29 29 29 29 curing accelerator 2P4MHZ-PW 2.0 2.0 2.0 2.0 2.0 coupling agent KBM-403 3.0 3.0 3.0 4.0 6.0 KBM-803 1.0 1.0 0.5 0.5 1.0 KBM-5803 1.5 1.5 1.5 1.5 1.5 release agent Powder Base L 6.0 5.0 5.0 5.0 5.0 Licowax-OP 2.0 2.0 2.0 2.0 2.0 additive DBL-C32 30 30 30 30 30 metal powder 9A4-II 4314 4292 4281 4303 4358 AW2-08 947 942 940 944 957 Metal powder content (mass %) 96.4 96.4 96.4 96.4 96.4 Flow Tester@130℃ Stroke length (mm) 10.6 10.6 10.7 10.7 9.7 Flow time (seconds) 17 18 18 19 17 Gel time@140℃(seconds) 250 240 245 245 230 250℃ bending elastic coefficient (GPa) 1.0 0.8 0.9 0.9 1.0 250℃ Bending Strength (MPa) 9.4 8.6 8.5 9.2 9.7 Reliability index (×10 ^-3 ) 9.9 10.3 9.6 10.2 9.4 Reflow evaluation A A A A A

【Table 2】 Comparative example 1 2 3 epoxy resin NC-3000 50 50 50 VG-3101L 50 50 50 Hardener HE910-09 twenty two twenty two twenty two MEHC-7841-4S 29 29 29 curing accelerator 2P4MHZ-PW 2.0 2.0 2.0 coupling agent KBM-403 - 3.0 - KBM-803 - 2.0 3.0 KBM-5803 1.5 - 1.5 release agent Powder Base L 6.0 5.0 5.0 Licowax-OP 2.0 2.0 2.0 additive DBL-C32 30 30 30 metal powder 9A4-II 4226 4281 4270 AW2-08 928 940 937 Metal powder content (mass %) 96.4 96.4 96.4 Flow Tester@130℃ Stroke length (mm) 10.7 7.5 9.0 Flow time (seconds) 13 31 30 Gel time@140℃(seconds) 250 210 220 250℃ bending elastic coefficient (GPa) 0.7 1.1 0.8 250℃ Bending Strength (MPa) 6.5 10.6 8.7 Reliability index (×10 ^-3 ) 9.0 9.3 10.3 Reflow evaluation B A A

Claims (9)

A compound comprising metal powder and a resin composition containing an epoxy resin, a curing agent and a coupling agent, The coupling agent includes a first silane compound and a second silane compound, the first silane compound has a functional group selected from an epoxy group, an amine group, a urea group and an isocyanate group, and the second silane compound has a carbon number of 6 or more the chain hydrocarbon group, Content of the said metal powder is 90 mass % or more and less than 100 mass %. The complex of claim 1, wherein The said coupling agent further contains the 3rd silane compound which has a mercapto group. A compound as claimed in claim 1 or claim 2, wherein The said 1st silane compound has an epoxy group. The complex of any one of claim 1 to claim 3, wherein The aforementioned second silane compound has a styryl group, a (meth)acryloyl group, or a vinyl group. The complex of any one of claim 1 to claim 4, wherein Content of the said coupling agent is 1.0 mass parts or more and 20 mass parts or less with respect to 100 mass parts of said epoxy resins. The complex of any one of claim 1 to claim 5, wherein The aforementioned metal powder contains at least one metal element selected from the group consisting of iron, cobalt, and nickel. The complex of any one of claim 1 to claim 6, wherein The aforementioned metal powder is a magnetic powder. A shaped body comprising the composite of any one of Claims 1 to 7. A cured product, which is a cured product of the composite according to any one of claim 1 to claim 7.