WO2022050170A1

WO2022050170A1 - Compound material, molded body, and cured product of compound material

Info

Publication number: WO2022050170A1
Application number: PCT/JP2021/031378
Authority: WO
Inventors: 翔平山口; 貴一稲葉
Original assignee: 昭和電工マテリアルズ株式会社
Priority date: 2020-09-03
Filing date: 2021-08-26
Publication date: 2022-03-10
Also published as: TW202219168A; JPWO2022050170A1; KR20230061411A; CN116134084A

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

Compounds, moldings, and cured products of compounds

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

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

Japanese Unexamined Patent Publication No. 2014-13803

When an industrial product is manufactured from a compound, the compound is supplied and filled into the mold through a flow path, and parts such as coils are embedded in the compound in the mold. The fluidity of the compound is required in these steps. The fluidity of the compound improves as the content of the metal powder in the compound decreases, but in order to improve the magnetic properties of the compound used for inductors and the like, the content of the metal powder in the compound (filling rate) ) Is desirable. However, as the content of the metal powder in the compound increases, the melt viscosity of the compound increases and the fluidity of the compound decreases. Further, in the step of heating the molded product made from the compound, cracks may be formed in the molded product. Therefore, the compound is required to have excellent fluidity during molding and to improve the mechanical properties (for example, high temperature bending properties) of the molded product at high temperature.

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

The compound according to one aspect of the present invention comprises a metal powder and a resin composition containing an epoxy resin, a curing agent, and a silane coupling agent, wherein the silane coupling agent is an epoxy group, an amino group, or a ureido group. , And a first silane compound having a functional group selected from an isocyanate group and a second silane compound having a chain hydrocarbon group having 6 or more carbon atoms, and the content of the metal powder is 90% by mass. It is less than 100% by mass.

The molded product according to one aspect of the present invention contains the above compound. The cured product according to one aspect of the present invention is a cured product of the above compound.

According to the present invention, there is provided a compound capable of forming a molded product having excellent fluidity during molding and excellent mechanical properties at high temperatures, a molded product using the same, and a cured product of the compound.

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

[compound]
The compound according to the present 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 elemental metals, 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 having a functional group selected from an epoxy group, an amino group, a ureido group, and an isocyanate group, and a second silane compound having a chain hydrocarbon group having 6 or more carbon atoms. including. In the compound, the metal powder, the epoxy resin, the curing agent, and the 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 is a component that can include an epoxy resin, a curing agent, a coupling agent, a curing accelerator, a mold release agent, and an additive, and is a component other than an organic solvent and a metal powder, and is a remaining component (nonvolatile component). ) May be. The additive is a component of the rest of the resin composition excluding the resin, the mold release agent, the curing agent, the curing accelerator, and the coupling agent. Additives are, for example, flame retardants, lubricants and the like. The compound may be a powder (compound powder).

The compound may include a metal powder and a resin composition attached to the surface of each metal particle constituting the metal powder. The resin composition may cover the entire surface of the particles, or may cover only a part of the surface of the particles. The compound may comprise an uncured resin composition and a metal powder. The compound may include a semi-cured product of the resin composition (for example, a B-stage resin composition) and a metal powder. The compound may comprise both an uncured resin composition and a semi-cured resin composition. The compound may consist of a metal powder and a resin composition.

The content of the metal powder in the compound is 90% by mass or more and less than 100% by mass with respect to the total mass of the compound. When the content of the metal powder is large, it is difficult to ensure the releasability of the molded product, and the workability tends to be inferior. From the viewpoint of the magnetic properties of the molded product, the content of the metal powder is preferably 92% by mass or more, more preferably 94% by mass or more, further preferably 95% by mass or more, and particularly preferably 96% by mass or more. The upper limit of the content of the metal powder may be 99% by mass or less, 98% by mass or less, or 97.5% by mass or less.

(Resin composition)
The resin composition has a function as a binder of metal particles constituting the metal powder, and imparts mechanical strength to the molded product formed from the compound. For example, the resin composition contained in the compound is filled between the metal particles when the compound is molded at high pressure using a mold, and the particles are bound to each other. By curing the resin composition in the molded product, the cured product of the resin composition binds the metal particles more firmly to each other, and the mechanical strength of the molded product is improved.

The resin composition according to this embodiment contains an epoxy resin as a thermosetting resin, so that the fluidity of the compound can be improved. The epoxy resin may be, for example, a resin having two or more epoxy groups in one molecule. The type of epoxy resin is not particularly limited and can be selected according to the desired properties of the composition and the like.

Examples of the epoxy resin include biphenyl type epoxy resin, stillben type epoxy resin, diphenylmethane type epoxy resin, sulfur atom-containing epoxy resin, novolak type epoxy resin, dicyclopentadiene type epoxy resin, salicylaldehyde type epoxy resin, naphthols and phenol. Copolymerization type epoxy resin, aralkyl type phenol resin epoxidized product, bisphenol type epoxy resin, epoxy resin containing bisphenol skeleton, alcoholic glycidyl ether type epoxy resin, paraxylylene and / or metaxylylene modified phenol resin glycidyl ether Type epoxy resin, glycidyl ether type epoxy resin of terpene-modified phenol resin, cyclopentadiene type epoxy resin, glycidyl ether type epoxy resin of polycyclic aromatic ring-modified phenol resin, glycidyl ether type epoxy resin of naphthalene ring-containing phenol resin, glycidyl ester type Epoxy resin, glycidyl type or methyl glycidyl type epoxy resin, alicyclic epoxy resin, halogenated phenol novolac type epoxy resin, orthocresol novolac type epoxy resin, hydroquinone type epoxy resin, trimethylolpane type epoxy resin, and olefin bond Examples thereof include a linear aliphatic epoxy resin obtained by oxidizing with a peracid such as peracetic acid.

From the viewpoint of fluidity, the epoxy resins include biphenyl type epoxy resin, orthocresol novolac type epoxy resin, phenol novolac type epoxy resin, bisphenol type epoxy resin, epoxy resin having a bisphenol skeleton, salicylaldehyde novolak type epoxy resin, and naphthol novolac. It may contain at least one selected from the group consisting of type epoxy resins.

From the viewpoint of mechanical strength, the epoxy resin may contain at least one selected from the group consisting of biphenylene aralkyl type epoxy resin and orthocresol 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, at least one selected from the group consisting of a hydroquinone type epoxy resin, a bisphenol type epoxy resin, a thioether type epoxy resin, and a biphenyl type epoxy resin. ..

Commercially available crystalline epoxy resins include, for example, Epicron 860, Epicron 1050, Epicron 1055, Epicron 2050, Epicron 3050, Epicron 4050, Epicron 7050, Epicron HM-091, Epicron HM-101, Epicron N-730A, Epicron. N-740, Epicron N-770, Epicron N-775, Epicron N-865, Epicron HP-4032D, Epicron HP-7200L, Epicron HP-7200, Epicron HP-7200H, Epicron HP-7200HH, Epicron HP-7200HH, Epicron HP-4700, Epicron HP-4710, Epicron HP-4770, Epicron HP-5000, Epicron HP-6000, N500P-2, and N500P-10 (above, trade name manufactured by DIC Co., Ltd.); NC-3000, NC- 3000-L, NC-3000-H, NC-3100, CER-3000-L, NC-2000-L, XD-1000, NC-7000-L, NC-7300-L, EPPN-501H, EPPN-501HY, EPPN-502H, EOCN-1020, EOCN-102S, EOCN-103S, EOCN-104S, CER-1020, EPPN-201, BREN-S, and BREN-10S (above, trade name manufactured by Nippon Kayaku Co., Ltd.); Examples thereof include YX-4000, YX-4000H, YL4121H, and YX-8800 (hereinafter, trade names manufactured by Mitsubishi Chemical Corporation).

The resin composition may contain one of the above epoxy resins. The resin composition may contain a plurality of types of epoxy resins among the above. Among the above epoxy resins, the resin composition may contain an epoxy resin containing a biphenyl skeleton, an orthocresol novolac type epoxy resin, or a polyfunctional epoxy resin containing two or more epoxy groups.

The curing agent is classified into a curing agent that cures the epoxy resin in the range of low temperature to room temperature and a heat curing type curing agent that cures the epoxy resin with heating. The curing agent that cures the epoxy resin in the range of low temperature to room temperature is, for example, aliphatic polyamines, polyaminoamides, and polymercaptans. The heat-curing type curing agent is, for example, aromatic polyamine, acid anhydride, phenol novolac resin, dicyandiamide (DICY) and the like. The type 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 the epoxy resin in the range from low temperature to room temperature is used, the glass transition point of the cured product of the epoxy resin is low, and the cured product of the epoxy resin tends to be soft. As a result, the molded product formed from the compound also tends to be soft. On the other hand, from the viewpoint of improving the heat resistance of the molded product, the curing agent may be preferably a heat-curing type curing agent, more preferably a phenol resin, and further preferably a phenol novolac resin. In particular, by using a phenol novolac resin as a curing agent, it is easy to obtain a cured product of an epoxy resin having a high glass transition point. As a result, the heat resistance and mechanical strength of the molded product are likely to be improved.

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

The phenol 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 include, for example, at least one selected from the group consisting of phenol, cresol, xylenol, resorcin, catechol, bisphenol A, bisphenol F, phenylphenol, and aminophenol. 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 novolac resin may contain, for example, at least one selected from the group consisting of formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde, and salicylaldehyde.

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

The resin composition may contain one of the above phenolic resins. The resin composition may include a plurality of types of phenol resins among the above. The resin composition may contain one of the above-mentioned curing agents. The resin composition may contain a plurality of types of curing agents among the above.

The ratio of the active group (phenolic OH group) in the curing agent that reacts with the epoxy group in the epoxy resin is preferably 0.5 to 1.5 equivalents, more preferably 0.5 to 1.5 equivalents with respect to 1 equivalent of the epoxy group in the epoxy resin. May be 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 of the molded product formed from the compound after curing tends to decrease. However, even when the ratio of the active group in the curing agent is out of the above range, the effect according to the present invention can be obtained.

The coupling agent can improve the adhesion between the resin composition and the metal element-containing particles constituting the metal powder, and can improve the flexibility and mechanical strength of the molded product formed from the compound. By containing a specific silane compound as a coupling agent, the resin composition according to the present embodiment can improve the fluidity and curing characteristics of the compound. The coupling agent includes a first silane compound having a functional group selected from an epoxy group, an amino group, a ureido group, and an isocyanate group, and a second silane compound having a chain hydrocarbon group having 6 or more carbon atoms. including. 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 containing the first silane compound in the resin composition, it is possible to form a molded product having excellent high temperature bending characteristics. The functional group of the first silane compound can react with the epoxy resin or the curing agent. The first silane compound is a silane compound having no long-chain hydrocarbon group.

Examples of the first silane compound having an epoxy group include 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, and 3-glycidoxypropylmethyl. Examples thereof include dimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltrimethoxysilane, and 3-glycidoxypropyltriethoxysilane.

Examples of the first silane compound having an amino group include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, and N-2-. (Aminoethyl) -3-aminopropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldiethoxysilane, N- Examples thereof include 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, 3-ureidopropylmethyldimethoxysilane, and 3-ureidopropylmethyldiethoxysilane.

Examples of the first silane compound having an isocyanate group include 3-isocyanatepropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, 3-isocyanatepropylmethyldimethoxysilane, and 3-isocyanatepropylmethyldiethoxysilane. ..

The content of the first silane compound is 0.5 parts by mass or more and 10 parts by mass or less and 1.0 part by mass or more and 8.0 parts by mass with respect to 100 parts by mass of the epoxy resin from the viewpoint of further improving the high temperature bending characteristics. It may be 2 parts or less, or 2.0 parts by mass or more and 7.0 parts by mass or less.

By containing the second silane compound in the resin composition, the fluidity during molding of the compound can be improved. The chain hydrocarbon group of the second silane compound has 6 or more carbon atoms, 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, heptiltrimethoxysilane, heptiltriethoxysilane, octyltrimethoxysilane, octyltriethoxysilane, dodecyltrimethoxysilane, and dodecyltriethoxysilane. , Acryloxyhexyltrimethoxysilane, acryloxyhexyltriethoxysilane, methacryoxyhexyltrimethoxysilane, methacryoxyhexyltriethoxysilane, acryloxy heptilt remethoxysilane, acryloxy heptilt reethoxysilane, methacryloxyl trimethoxysilane, Examples thereof include methacryloxyheptilt diethoxysilane, acryloxyoctyl trimethoxysilane, acryloxyoctyl triethoxysilane, methacryoxyoctyl trimethoxysilane, and methacryoxyoctyl diethoxysilane.

The content of the second silane compound is 0.1 parts by mass or more and 5.0 parts by mass or less and 0.5 parts by mass or more and 4.0 with respect to 100 parts by mass of the epoxy resin from the viewpoint of further improving the fluidity. It may be 1 part by mass or less, or 1.0 part by mass or more and 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 having no long-chain hydrocarbon group. Examples of the third silane compound include 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, and 3-mercaptopropylmethylditoxysilane.

The content of the coupling agent is 1.0 part by mass or more and 20 parts by mass or less and 2.0 parts by mass or more and 15 parts by mass or less with respect to 100 parts by mass of the epoxy resin from the viewpoint of achieving both fluidity and mechanical properties. , Or 3.0 parts by mass or more and 10 parts by mass or less.

The curing accelerator is not limited as long as it is a composition that reacts with the epoxy resin to accelerate the curing of the epoxy resin, for example. 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 mold releasability of the compound can be improved. Further, when the resin composition contains a curing accelerator, the mechanical strength of the molded product (for example, an electronic component) manufactured by using the compound is improved, and the compound is stored in a high temperature and high humidity environment. Stability is improved.

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

Commercially available imidazole-based curing accelerators include, for example, 2MZ-H, C11Z, C17Z, 1,2DMZ, 2E4MZ, 2PZ-PW, 2P4MZ, 1B2MZ, 1B2PZ, 2MZ-CN, C11Z-CN, 2E4MZ-CN, 2PZ. -At least one selected from the group consisting of CN, C11Z-CNS, 2P4MHZ, TPZ, and SFZ (above, trade name manufactured by Shikoku Chemicals Corporation) may be used.

The urea-based curing accelerator is not particularly limited as long as it is a curing accelerator having a urea group, but from the viewpoint of improving storage stability, an alkyl urea-based curing accelerator having an alkyl urea group is preferable. Examples of the alkylurea-based curing accelerator having an alkylurea group include aromatic alkylurea and aliphatic alkylurea. Examples of commercially available alkylurea-based curing accelerators include U-CAT3512T (trade name, manufactured by San-Apro Co., Ltd., aromatic dimethyl urea) and U-CAT3513N (trade name, manufactured by San-Apro Co., Ltd., aliphatic dimethyl urea). Can be mentioned. Among these, aromatic alkylurea is preferable because the cleavage temperature is moderately low and the compound can be easily cured efficiently.

The amount of the curing accelerator to be blended is not particularly limited as long as it can obtain the curing promoting effect. From the viewpoint of improving the curability and fluidity of the resin composition during moisture absorption, the amount of the curing accelerator is preferably 0.1 part by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the epoxy resin. It may be preferably 0.5 parts by mass or more and 15 parts by mass or less, and more preferably 1.0 part by mass or more and 10 parts by mass or less. When the blending amount of the curing accelerator is 0.1 part by mass or more, a sufficient curing promoting effect can be easily obtained. When the blending amount of the curing accelerator is 30 parts by mass or less, the storage stability of the compound is unlikely to decrease. The content of the curing accelerator is preferably 0.001 part by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the total mass of the epoxy resin and the phenol resin. However, even when the blending amount and content of the curing accelerator are out of the above range, the effect according to the present invention can be obtained.

The resin composition may contain a compound having a siloxane bond (siloxane compound) as an additive because the molding shrinkage of the compound is easily reduced and the heat resistance and withstand voltage of the molded product are easily improved. The siloxane bond is a bond containing two silicon atoms (Si) and one oxygen atom (O), and may 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.

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

When forming a molded product from a compound using a mold, the resin composition may contain wax. The wax enhances the fluidity of the compound in the molding of the compound (for example, transfer molding) and functions as a mold release agent. The wax may be at least one of a fatty acid such as a higher fatty acid and a fatty acid ester.

The wax is, for example, fatty acids such as montanic acid, stearic acid, 12-oxystearic acid, lauric acid or esters thereof; zinc stearate, calcium stearate, barium steaenoate, aluminum stearate, magnesium stearate, calcium laurate, laurin. Fatal acid salts such as zinc acid, zinc linoleate, calcium lysinoate, zinc 2-ethylhexoate; stearic acid amide, oleic acid amide, erucic acid amide, behenic acid amide, palmitate amide, lauric acid amide, hydroxystearic acid amide, Methylene bisstearic acid amide, ethylene bisstearic acid amide, ethylene bislauric acid amide, distealyl adipic acid amide, ethylene bisoleic acid amide, diorail adipic acid amide, N-stearyl stearic acid amide, N-oleyl stearic acid amide, Fatty acid amides such as N-stearyl erucate amide, methylol stearic acid amide, methylol behenic acid amide; fatty acid esters such as butyl stearate; alcohols such as ethylene glycol and stearyl alcohol; polyethylene glycol, polypropylene glycol, polytetramethylene glycol and Polyethers composed of these modified products; polysiloxanes such as silicone oil and silicon grease; fluorine compounds such as fluorine-based oil, fluorine-based grease and fluorine-containing resin powder; and paraffin wax, polyethylene wax, amido wax and polypropylene. It may be at least one selected from the group consisting of waxes such as wax, ester wax, carnauba, and microwax.

The wax content is 1 part by mass or more and 20 parts by mass or less, or 2 parts by mass or more and 15 parts by mass or less, or 3 parts by mass with respect to 100 parts by mass of the epoxy resin from the viewpoint of achieving both fluidity and releasability. It may be 10 parts by mass or less.

(Metal powder)
The metal powder (particle containing a metal element) may contain, for example, at least one selected from the group consisting of elemental metals, alloys and metal compounds. The metal element-containing powder may consist of, for example, at least one selected from the group consisting of elemental metals, alloys and metal compounds. The alloy may contain at least one selected from the group consisting of solid solutions, eutectic and intermetallic compounds. The alloy may be, for example, stainless steel (Fe—Cr based alloy, Fe—Ni—Cr based alloy, etc.). The metal compound may be, for example, an oxide such as ferrite. The metal powder may contain one kind of metal element or a plurality of kinds 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 compound may contain one kind of metal element-containing powder, and may contain a plurality of kinds of metal element-containing powders having different compositions.

The metal elements contained in the metal powder are, for example, iron (Fe), copper (Cu), titanium (Ti), manganese (Mn), cobalt (Co), nickel (Ni), zinc (Zn), and aluminum (Al). , Tin (Sn), Chromium (Cr), Niob (Nb), Barium (Ba), Strontium (Sr), Lead (Pb), Silver (Ag), Placeodim (Pr), Neodim (Nd), Samarium (Sm) , And dysprosium (Dy), which may be at least one selected from the group. From the viewpoint of improving the magnetic properties, the metal powder preferably contains at least one metal element selected from the group consisting of iron, cobalt, and nickel. The metal powder may further contain an element other than the metal element. 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 a magnetic powder. The metal powder may be a soft magnetic alloy or a ferromagnetic alloy. The metal powder is, for example, Fe-Si alloy, Fe—Si—Al alloy (Sendust), Fe—Ni alloy (Permalloy), Fe—Cu—Ni alloy (Permalloy), Fe—Co alloy (Permalloy). Menzur), Fe-Cr-Si alloy (electromagnetic stainless steel), Nd-Fe-B alloy (rare earth magnet), Sm-Fe-N alloy (rare earth magnet), Al-Ni-Co alloy (Arnico) It may be a magnetic powder consisting of at least one selected from the group consisting of (magnet) and ferrite. The ferrite may be, for example, spinel ferrite, hexagonal ferrite, or garnet ferrite. The metal powder may 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 elements and compositions, and may contain a plurality of of the above elements and compositions.

The metal powder may be Fe alone. 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 an Nd—Fe—B based alloy. The metal element-containing powder may be at least one of amorphous iron powder and carbonyl iron powder. When the metal powder contains at least one of Fe simple substance and Fe-based alloy, it is easy to produce a molded product having a high space factor and excellent magnetic properties from the compound. The metal powder may be an Fe amorphous alloy.

Commercially available Fe amorphous alloy powders include, for example, AW2-08, KUAMET-6B2 (above, trade name manufactured by Epson Atmix Co., Ltd.), DAP MS3, DAP MS7, DAP MSA10, DAP PB, DAP PC, DAP MKV49. , DAP 410L, DAP 430L, DAP HYB series (above, product name manufactured by Daido Special Steel Co., Ltd.), MH45D, MH28D, MH25D, and MH20D (above, product name manufactured by Kobe Steel Co., Ltd.). At least one may be used.

<Manufacturing method of compound>
In the production of the compound, 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 may be kneaded with a kneader, a roll, a stirrer, or the like while heating. 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 to cover the metal element-containing particles, and the epoxy in the resin composition. Part or all of the resin becomes a semi-cured product. The result is a compound. A compound may 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 the wax may be mixed in advance.

In kneading, metal powder, epoxy resin, curing agent, curing accelerator, and coupling agent may be kneaded in the tank. After the metal powder and the coupling agent are charged into the tank and mixed, the epoxy resin, the curing agent, and the curing accelerator may be charged into the tank to knead the raw materials in the tank. After kneading the siloxane compound, the epoxy resin, the curing agent, and the coupling agent in the tank, the curing accelerator may be put in the tank, and the raw materials in the tank may be further kneaded. A mixed powder of an epoxy resin, a curing agent, and a curing accelerator (resin mixed powder) is prepared in advance, and then the metal powder and the coupling agent are kneaded to prepare a metal mixed powder, and then the metal. The mixed powder and the above-mentioned resin mixed powder may be kneaded.

The kneading time depends on the type of the kneading machine, the volume of the kneading machine, and the production amount of the compound, but for example, it is preferably 1 minute or more, more preferably 2 minutes or more, and 3 minutes or more. Is more preferable. The kneading time is preferably 20 minutes or less, more preferably 15 minutes or less, and even more preferably 10 minutes or less. If the kneading time is less than 1 minute, the kneading is insufficient, the moldability of the compound is impaired, and the degree of curing of the compound 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 compound are easily impaired.

When the raw materials in the tank are kneaded with a kneader while heating, the heating temperature is, for example, a semi-cured epoxy resin (B-stage epoxy resin) and a cured epoxy resin (C-stage epoxy resin). It suffices as long as it is a temperature at which the formation of the epoxy is suppressed. 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 softens and easily covers the surface of the metal element-containing particles constituting the metal powder, and a semi-cured epoxy resin is easily produced, and is being kneaded. Complete curing of the epoxy resin is likely to be suppressed.

[Molded product]
The molded product according to the present embodiment may be provided with the above-mentioned compound. The molded product according to the present embodiment may be provided with a cured product of the above compound. The molded product is 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). May include. The molded product according to this embodiment may be used as a sealing material for electronic components or electronic circuit boards. According to this embodiment, it is possible to suppress cracks in the molded body due to the difference in the coefficient of thermal expansion between the metal member included in the electronic component or the electronic circuit board and the molded body (sealing material).

The cured product of the compound 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. The bending 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, from the viewpoint of increasing the strength of the cured product. The upper limit of the bending strength is about 10 MPa. The flexural modulus of the cured product at 250 ° C. may be 1.3 GPa or less, 1.2 GPa or less, or 1.1 GPa or less from the viewpoint of imparting flexibility to the cured product. The lower limit of the flexural modulus is about 0.1 GPa. The value obtained by dividing the bending strength (MPa) at 250 ° C. by the flexural modulus (GPa) at 250 ° C. can be used as an index of the reliability of the cured product. The index is preferably 9.0 × 10 ^-3 or more, more preferably 9.2 × 10 ^-3 or more, and further preferably 10.4 × 10 ^-3 or more. The upper limit of the index is not particularly limited, and may be, for example, 5 × ^10-2 or less.

<Manufacturing method of molded product>
The method for producing a molded product according to the present embodiment may include a step of pressurizing the compound in a mold. The method for producing a molded product may include a step of pressurizing a compound covering a part or the whole of the surface of a metal member in a mold. The method for producing a molded product may include only a step of pressurizing the compound in a mold, and may include other steps in addition to the step. The method for producing the molded product may include a first step, a second step, and a third step. Hereinafter, the details of each step will be described.

In the first step, the compound is prepared by the above method.

In the second step, a molded product (B stage molded product) is obtained by pressurizing the compound in a mold. In the second step, a molded product (B stage molded product) may be obtained by pressurizing a compound covering a part or the entire surface of the metal member in a mold. In the second step, the resin composition is filled between the individual metal element-containing particles constituting the metal element-containing powder. The resin composition then functions as a binder and binds the metal element-containing particles to each other.

As the second step, transfer molding of the compound may be carried out. In transfer molding, the compound may be pressurized at 5 MPa or more and 50 MPa or less. The higher the molding pressure, the easier it is to obtain a molded product having excellent mechanical strength. Considering the mass productivity of the molded product 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 product formed by transfer molding may be preferably 75% or more and 86% or less, and more preferably 80% or more and 86% or less with respect to the true density of the compound. When the density of the molded product is 75% or more and 86% or less, it is easy to obtain a molded product having excellent mechanical strength. In the transfer molding, the second step and the third step may be carried out collectively.

In the third step, the molded product is cured by heat treatment to obtain a C-stage molded product. The temperature of the heat treatment may be any temperature as long as the resin composition in the molded product 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 molded product, 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 cured resin product is deteriorated by a small amount of oxygen inevitably contained in the heat treatment atmosphere. In order to sufficiently cure the resin composition while suppressing the oxidation of the metal powder and the deterioration of the cured resin product, the heat treatment temperature holding time is preferably several minutes or more and 10 hours or less, more preferably 3 minutes or more 8 It may be less than an hour.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these examples.

Details of each component used in the preparation of the compounds 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 Co., Ltd., epoxy equivalent: 215 g / eq)

(Hardener)
Triphenylmethane type phenol resin (trade name: HE910-09 manufactured by Air Water Inc., hydroxyl group equivalent: 101 g / eq)
Biphenylene aralkyl type phenol resin (trade name: MEHC-7841-4S manufactured by Meiwa Kasei Co., Ltd., hydroxyl group equivalent: 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.)
Methacryloxyoctyltrimethoxysilane (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 montanic acid ester wax (trade name: Licowax-OP manufactured by Clariant Chemicals Co., Ltd.)
(Additive)
Caprolactone-modified dimethyl silicone (trade name: DBL-C32 manufactured by Gelest Co., Ltd.)

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

[Preparation of compound]
(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 blending amounts (unit: g) shown in the same table. A resin mixture was prepared by mixing these materials in a plastic container for 10 minutes. The resin mixture corresponds to all the other components of the resin composition except the coupling agent and the additive.

The two types of amorphous iron powder shown in Table 1 were uniformly mixed for 5 minutes with a pressurized twin-screw kneader (manufactured by Nihon Spindle Manufacturing Co., Ltd., capacity 5 L) to prepare a metal powder. The coupling agents and additives shown in Table 1 were added to the metal powder in the twin-screw kneader. Subsequently, the contents of the twin-screw kneader were heated to 90 ° C., and the contents of the twin-screw kneader were mixed for 10 minutes while maintaining the temperature. Subsequently, the above resin mixture was added to the contents of the twin-screw kneader, and the contents were melted and kneaded for 15 minutes while maintaining the temperature of the contents at 120 ° C. After cooling the kneaded product obtained by the above melting and kneading to room temperature, the kneaded product was crushed with a hammer until the kneaded product had a predetermined particle size. The above-mentioned "melting" means melting at least a part of the resin composition in the contents of the twin-screw kneader. The metal powder in the compound does not melt during the compound preparation process. The compounds of Examples 1 to 5 were prepared by the above method.

(Comparative Examples 1 to 3)
The compounds of Comparative Examples 1 to 3 were prepared by operating in the same manner as in Examples except that the types and blending amounts of each component were changed as shown in Table 2.

[Compound evaluation]
The compounds obtained in Examples and Comparative Examples were evaluated as follows. The results are shown in Tables 1 and 2.

(Liquidity)
The liquidity was evaluated using a flow tester CFT-100 manufactured by Shimadzu Corporation. A tablet was prepared by molding 7 g of the compound. Using a tablet, the fluidity was evaluated under the conditions of 130 ° C., residual heat of 20 seconds, and load of 100 kg. The pushing distance (unit: mm) of the plunger until the flow of the compound stopped was used as the flow tester stroke, and the time until the flow of the compound stopped was measured as the flow time, which was used as an index of the liquidity.

(Gel time)
The gel time of the compound was measured by the following method. The gel time was measured using a curast meter (manufactured by JSR Trading Co., Ltd.) under the conditions of a sample volume of 1.5 mL and 140 ° C. The time at which the torque of the obtained chart started to rise was defined as the gel time. The shorter the gel time, the higher the curability.

(Bending test)
The compound 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, and then post-cured at 180 ° C. for 2 hours to obtain a test piece. The dimensions of the test piece were 80 mm in length × 10 mm in 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 at 250 ° C. As the autograph, 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 central 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 for the bending test were as follows.
Distance between two fulcrums Lv: 64.0 ± 0.5 mm
Head speed: 2.0 ± 0.2 mm / min Chart speed: 100 mm / min Chart full scale: 490N (50 kgf)

The bending strength σ (unit: MPa) was calculated based on the following mathematical formula (A). The flexural modulus E (unit: GPa) was calculated based on the following mathematical 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 width (unit: mm) of the test piece. “T” is the thickness (unit: mm) of the test piece. "F / Y" is the gradient (unit: N / mm) of the straight line 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 bending strength (MGa) at 250 ° C. by the flexural modulus (GPa) at 250 ° C. was used as an index for evaluating reliability. The larger this value is, the better the balance between strength and elastic modulus is.

(Reflow processing)
By transfer molding, a copper metal member was sealed with a compound, and the compound was cured to obtain a molded product. The molded body was reflowed. The maximum heating temperature in the reflow treatment was 260 ° C. The heating time was 300 seconds. After the reflow treatment, the molded product was observed to check for cracks in the molded product. "A" in the table means that the crack was not formed in the molded body, and "B" means that the crack was formed in the molded body.

Claims

A resin composition containing a metal powder, an epoxy resin, a curing agent, and a coupling agent is provided.
The coupling agent is a first silane compound having a functional group selected from an epoxy group, an amino group, a ureido group, and an isocyanate group, and a second silane compound having a chain hydrocarbon group having 6 or more carbon atoms. Including and
A compound having a metal powder content of 90% by mass or more and less than 100% by mass.
The compound according to claim 1, wherein the coupling agent further contains a third silane compound having a mercapto group.
The compound according to claim 1 or 2, wherein the first silane compound has an epoxy group.
The compound according to any one of claims 1 to 3, wherein the second silane compound has a styryl group, a (meth) acryloyl group, or a vinyl group.
The compound according to any one of claims 1 to 4, wherein the content of the coupling agent is 1.0 part by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the epoxy resin.
The compound according to any one of claims 1 to 5, wherein the metal powder contains at least one metal element selected from the group consisting of iron, cobalt, and nickel.
The compound according to any one of claims 1 to 6, wherein the metal powder is a magnetic powder.
A molded product containing the compound according to any one of claims 1 to 7.
The cured product of the compound according to any one of claims 1 to 7.