KR20230017227A - Compounds, Molded Products, and Cured Products - Google Patents

Abstract

A compound comprising a resin composition containing a metal powder, an epoxy resin, a curing agent and a dispersing agent, wherein the content of the metal powder is 90% by mass or more and 98% by mass or less, and the dispersing agent contains a phosphate ester.

Description

Compounds, Molded Products, and Cured Products

The present invention relates to compounds, molded products, and cured products.

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

Patent Document 1: Japanese Unexamined Patent Publication No. 2014-13803

In the case of manufacturing industrial products with a compound, the compound is supplied and charged into the mold through a flow path, or parts such as coils are embedded in the compound in the mold. In these processes, fluidity of the compound is required. However, when the content of the metal powder in the compound increases, the fluidity of the compound is significantly reduced, and it becomes difficult to fill the compound into the mold. [0002] With the recent miniaturization of electronic devices, the dimensions of elements mounted on electronic devices are becoming smaller. Therefore, when using a compound for manufacturing an element, it is necessary for the compound to flow in a narrow flow path and to uniformly fill the compound that has passed through the narrow flow path into a fine mold.

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

The compound according to one aspect of the present invention includes a resin composition containing a metal powder, an epoxy resin, a curing agent and a dispersing agent, the content of the metal powder is 90% by mass or more and 98% by mass or less, and the dispersing agent contains a phosphoric acid ester do.

In one aspect, the phosphoric acid ester may have a group represented by -OR (R represents an organic group having 4 or more carbon atoms).

In one aspect, the organic group may be an alkyl group having 4 or more carbon atoms or an ether bond inserted into at least a part of the carbon-carbon bonds in the alkyl group having 4 or more carbon atoms.

In one aspect, an alkyl group and a group in which an ether bond is inserted into at least a part of the carbon-carbon bonds in the alkyl group may have a substituent.

In one aspect, the content of the dispersant may be 1 part by mass or less with respect to 100 parts by mass of the metal powder.

A molded article according to one aspect of the present invention includes the compound.

A cured product according to one aspect of the present invention is a cured product of the compound.

According to the present invention, a compound having excellent fluidity can be provided. Moreover, according to this invention, the molded object and hardened|cured material containing the said compound can be provided. The compound of the present invention has low viscosity and excellent fluidity. Therefore, the compound can be filled into the mold with good filling properties.

Hereinafter, preferred embodiments of the present invention will be described. However, the present invention is by no means limited to the following embodiments.

[Compound]

The compound according to the present embodiment includes metal powder and a resin composition. Metal powder may contain at least 1 sort(s) chosen from the group which consists of a simple metal, an alloy, an amorphous powder, and a metal compound, for example. A resin composition contains at least an epoxy resin, a hardening|curing agent, and a dispersing agent. The dispersing agent contains phosphate ester. In the compound, metal powder, epoxy resin, curing agent and dispersing agent are mixed. The resin composition may further contain a hardening accelerator, a release agent, an additive, etc. as other components. The resin composition is a component that may contain an epoxy resin, a curing agent, a dispersing agent, a curing accelerator, a release agent, and an additive, and may be components (non-volatile components) other than the organic solvent and the metal powder. An additive is a component of the remainder except for an epoxy resin, a curing agent, a dispersing agent, a curing accelerator, and a mold release agent in a resin composition. Additives are, for example, coupling agents, siloxane compounds, flame retardants and the like. The compound may be powder (compound powder).

The compound may be provided with a metal powder and a resin composition adhering 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 compound may include an uncured resin composition and metal powder. The compound may include a semi-cured product of a resin composition (for example, a B-stage resin composition) and a metal powder. The compound may include both an uncured resin composition and a semi-cured product of the resin composition. The compound may consist of metal powder and a resin composition.

Content of the metal powder in a compound is 90 mass % or more and 98 mass % or less. The content of the metal powder in the compound may be preferably 92% by mass or more and 98% by mass or less, 94% by mass or more and 97.5% by mass or less, or 96% by mass or more and 97.5% by mass or less. If the content of the metal powder in the compound not containing a dispersant is 90% by mass or more, the fluidity of the compound is remarkably reduced. On the other hand, the compound according to the present embodiment contains a phosphate ester as a dispersant. As a result, even though the content of the metal powder in the compound is 90% by mass or more, the compound according to the present embodiment is superior to the conventional compound in fluidity.

The average particle diameter of the metal powder is not particularly limited, but may be, for example, 1 μm or more and 300 μm or less. The average particle diameter may be measured, for example, with a particle size distribution analyzer. Although the shape of each metal particle which comprises metal powder is not limited, For example, a spherical shape, a flat shape, a prismatic shape, or needle shape may be sufficient. A compound may be provided with multiple types of metal powders from which average particle diameters differ.

Depending on the composition or combination of metal powders included in the compound, all properties such as electromagnetic properties of molded and cured products formed from the compound can be freely controlled, so that the molded and cured products can be used as various industrial products or their raw materials. there is. Industrial products manufactured using the compound may be, for example, automobiles, medical equipment, electronic equipment, electric equipment, information communication equipment, home appliances, audio equipment, and general industrial equipment. For example, when the compound contains a permanent magnet such as a Sm-Fe-N-based alloy or a Nd-Fe-B-based alloy as metal powder, the compound may be used as a raw material for a bonded magnet. When the compound contains soft magnetic powder such as Fe-Si-Cr alloy or ferrite as metal powder, the compound is used as a raw material for an inductor (e.g. EMI filter) or transformer (e.g. magnetic core) It can be. When the compound contains iron and copper as metal powder, a molded article (for example, a sheet) formed of the compound may be used as an electromagnetic shield.

(resin composition)

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

The resin composition according to the present embodiment can improve the fluidity of the compound 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 type of epoxy resin is not particularly limited and may be selected according to desired characteristics of the composition and the like.

Epoxy resins include, for example, biphenyl-type epoxy resins, stilbene-type epoxy resins, diphenylmethane-type epoxy resins, sulfur atom-containing epoxy resins, novolac-type epoxy resins, dicyclopentadiene-type epoxy resins, and salicylyl. Aldehyde type epoxy resins, copolymer type epoxy resins of naphthols and phenols, epoxides of aralkyl type phenol resins, bisphenol type epoxy resins, epoxy resins containing a bisphenol skeleton, glycidyl ether type epoxy resins of alcohols, paraxylylene And / or glycidyl ether-type epoxy resins of metaxylylene-modified phenolic resins, glycidyl ether-type epoxy resins of terpene-modified phenolic resins, cyclopentadiene-type epoxy resins, polycyclic aromatic ring-modified phenolic resins in glycidyl Ter-type epoxy resins, glycidyl ether type epoxy resins of naphthalene ring-containing phenol resins, glycidyl ester type epoxy resins, glycidyl type or methyl glycidyl type epoxy resins, alicyclic type epoxy resins, halogenated phenol novolak type at least selected from the group consisting of epoxy resins, orthocresol novolac type epoxy resins, hydroquinone type epoxy resins, trimethylolpropane type epoxy resins, and linear aliphatic epoxy resins obtained by oxidizing olefin bonds with peracids such as peracetic acid; You may contain 1 type.

From the viewpoint of fluidity, the epoxy resin is a biphenyl type epoxy resin, an orthocresol novolac type epoxy resin, a phenol novolak type epoxy resin, a bisphenol type epoxy resin, an epoxy resin having a bisphenol skeleton, a salicylaldehyde novolac type epoxy It may contain at least 1 sort(s) selected from the group which consists of resin and a 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 biphenylene aralkyl type epoxy resins and orthocresol novolak type epoxy resins.

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 excellent fluidity. The crystalline epoxy resin (epoxy resin having high crystallinity) is, 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. may contain As commercially available products of crystalline epoxy resin, for example, Epiclone 860, Epiclone 1050, Epiclone 1055, Epiclone 2050, Epiclone 3050, Epiclone 4050, Epiclone 7050, Epiclone HM-091, Epiclone HM- 101, Epiclone N-730A, Epiclone N-740, Epiclone N-770, Epiclone N-775, Epiclone N-865, Epiclone HP-4032D, Epiclone HP-7200L, Epiclone HP-7200, Epiclone HP-7200H, Epiclone HP-7200HH, Epiclone HP-7200HHH, Epiclone HP-4700, Epiclone HP-4710, Epiclone HP-4770, Epiclone HP-5000, Epiclone HP-6000, N500P- 2, and N500P-10 (above, trade name manufactured by DIC Corporation), NC-3000, NC-3000-L, NC-3000-H, NC-3100, CER-3000-L, NC-2000-L, XD- 1000, NC-7000-L, NC-7300-L, EPPN-501H, EPPN-501HY, EPPN-502H, EOCN-1020, EOCN-102S, EOCN-103S, EOCN-104S, CER-1020, EPPN-201, BREN-S, BREN-10S (above, trade names manufactured by Nippon Kayaku Co., Ltd.), YX-4000, YX-4000H, YL4121H, and YX-8800 (above, trade names manufactured by Mitsubishi Chemical Corporation), VG3101L (above, trade names manufactured by Mitsubishi Chemical Corporation), VG3101L (above, Printec Co., Ltd.) product name) and the like.

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

The curing agent is classified into a curing agent that cures an epoxy resin in a range from low temperature to room temperature, and a heat curing type curing agent that cures an epoxy resin by heating. Curing agents that cure epoxy resins in the range from low temperature to room temperature include, for example, aliphatic polyamines, polyaminoamides, and polymercaptans. Heat-curable curing agents include, for example, aromatic polyamines, acid anhydrides, phenol novolak resins, and dicyandiamide (DICY). The type of curing agent is not particularly limited and may be selected according to desired characteristics of the composition and the like.

When a curing agent that cures an epoxy resin in a range from low temperature to room temperature is used, the cured product of the epoxy resin has a low glass transition point and the cured product of the epoxy resin tends to be soft. As a result, the molded article formed from the compound also tends to become soft. On the other hand, from the viewpoint of improving the heat resistance of the molded article, the curing agent is preferably a heat-curing type curing agent, more preferably a phenol resin, still more preferably a phenol novolac 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 is easily obtained. As a result, the heat resistance and mechanical strength of the molded article are likely to be improved.

Phenolic resins include, for example, aralkyl type phenol resins, dicyclopentadiene type phenol resins, salicylaldehyde type phenol resins, novolac type phenol resins, copolymerization type phenol resins of benzaldehyde type phenols and aralkyl type phenols, para Xylylene and/or metaxylylene-modified phenolic resins, melamine-modified phenolic resins, terpene-modified phenolic resins, dicyclopentadiene-type naphthol resins, cyclopentadiene-modified phenolic resins, polycyclic aromatic ring-modified phenolic resins, and biphenyl-type phenols You may contain at least 1 sort(s) selected from the group which consists of resin, a biphenylene aralkyl type phenol resin, and a triphenylmethane type phenol resin. The phenol resin may be a copolymer composed of two or more of the above. As commercially available products of the phenolic resin, for example, Tamanol 758 manufactured by Arakawa Chemical Industry Co., Ltd., HP-850N manufactured by Hitachi Chemical Co., Ltd., MEHC-7500-3S manufactured by Maywa Chemical Co., Ltd., MEHC-7851SS, etc. may be used. .

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

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 phenol resins. The resin composition may be provided with plural types of phenol resins among the above. The resin composition may contain one of the above curing agents. The resin composition may contain a plurality of types of curing agents among the above.

The ratio of active groups (phenolic OH groups) in the curing agent reacting with the epoxy groups in the epoxy resin is preferably 0.5 to 1.5 equivalents, more preferably 0.6 to 1.4 equivalents, and still more preferably 1 equivalent of the epoxy groups in the epoxy resin. 0.7 to 1.2 equivalents may be sufficient. When the ratio of the active groups in the curing agent is less than 0.5 equivalent, it is difficult to obtain a sufficient modulus of elasticity of the resulting cured product. On the other hand, when the ratio of the active groups in the curing agent exceeds 1.5 equivalents, the mechanical strength after curing of a molded article formed of a compound tends to decrease. However, even when the ratio of the active groups in the curing agent is outside the above range, the effects related to the present invention are obtained.

When the resin composition contains a dispersant containing a phosphoric acid ester, the fluidity of the compound can be improved. Thereby, unfilled at the time of molding and generation of voids in the molded body can be suppressed. The reason why the fluidity of the compound is improved is not necessarily clear, but the inventors speculate that the fluidity is improved because the phosphate group of the phosphate ester is selectively adsorbed to the metal powder, thereby improving the dispersibility of the metal powder.

A phosphoric acid ester is a compound represented by O=P(OH) _3-n (OR) _n (n=1 to 3). The phosphoric acid ester may be a phosphoric acid monoester, a phosphoric acid diester, or a phosphoric acid triester, but from the viewpoint of improving the fluidity of the compound, a phosphoric acid monoester or phosphoric acid diester in which n in the above formula is 1 or 2 may be used.

As a phosphoric acid ester, you may preferably have a group represented by -OR (R represents an organic group having 4 or more carbon atoms). When the number of carbon atoms of the organic group contained in the ester site is 4 or more, the fluidity of the compound is easily improved. From this point of view, the carbon number of R may be 5 or more, or 6 or more. Also, from the viewpoint of the dispersibility of the metal powder, the carbon number of R can be 20 or less, and may be 15 or less.

The organic group may be an alkyl group having 4 or more carbon atoms or an ether bond inserted into at least a part of the carbon-carbon bonds in the alkyl group having 4 or more carbon atoms. This makes it easy to improve the fluidity of the compound. The alkyl group may be a linear or branched alkyl group.

The alkyl group and the group in which an ether bond is inserted into at least a part of the carbon-carbon bonds in the alkyl group may have a substituent (reactive group). Thereby, compatibility of the resin and the dispersant in the resin composition is further improved. As a substituent, an amino group, a ureido group, an epoxy group, a thiol group, a (meth)acryloyl group, a hydroxyl group, etc. are mentioned. In addition, said "carbon number" in organic group R is a number which does not contain carbon number contained in a substituent.

As a commercial item of a phosphoric acid ester, JP-504, JP-506H, JP-508, JP-513 etc. by Johoku Chemical Industry Co., Ltd. are mentioned, for example.

Compound 1 represented by the following formula (1) may be, for example, JP-504.

Compound 2 represented by the following formula (2) may be, for example, JP-506H.

Compound 3 represented by the following formula (3) may be, for example, JP-508.

Compound 4 represented by the following formula (4) may be, for example, JP-513.

(C ₄ H ₉ O) _n OP(OH) _3-n (1)

1 or 2 may be sufficient as n in the said Formula (1). 1 or more and 3 or less may be sufficient as n in the said Formula (1).

(C ₄ H ₉ OCH ₂ CH ₂ O) _n OP(OH) _3-n (2)

1 or 2 may be sufficient as n in the said Formula (2). n in the formula (2) may be 1 or more and 3 or less.

(C ₄ H ₉ C ₂ H ₅ CHCH ₂ O) _n OP(OH) _3-n (3)

1 or 2 may be sufficient as n in the said Formula (3). 1 or more and 3 or less may be sufficient as n in the said Formula (3).

(iso-C ₁₃ H ₂₇ O) _n OP(OH) _3-n (4)

1 or 2 may be sufficient as n in the said Formula (4). n in the formula (4) may be 1 or more and 3 or less.

The blending amount of the dispersant may be 1 part by mass or less, 0.5 part by mass or less, 0.1 part by mass or less, or 0.05 part by mass or less with respect to 100 parts by mass of the metal powder from the viewpoint of improving the fluidity of the compound. From the same viewpoint, the blending amount may be 0.01 parts by mass or more.

The curing accelerator is not limited as long as it is a composition that reacts with an epoxy resin to accelerate 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. When the resin composition contains a curing accelerator, the moldability and releasability of the compound can be improved. In addition, when the resin composition contains a curing accelerator, the mechanical strength of molded products or cured products (e.g., electronic parts) produced using the compound is improved, and the storage stability of the compound in a high temperature and high humidity environment is improved. be or do

As a phosphorus hardening accelerator, a phosphine compound and a phosphonium salt compound are mentioned, for example.

Examples of commercially available imidazole curing accelerators include 2MZ-H, C11Z, C17Z, 1,2DMZ, 2E4MZ, 2PZ-PW, 2P4MZ, 1B2MZ, 1B2PZ, 2MZ-CN, C11Z-CN, 2E4MZ-CN, and 2PZ. -You may use at least 1 sort(s) selected from the group which consists of CN, C11Z-CNS, 2P4MHZ, TPZ, and SFZ (above, the trade name of Shikoku Kasei Kogyo Co., Ltd.).

The urea-based curing accelerator is not particularly limited as long as it is a curing accelerator having a urea group, but is preferably an alkylurea-based curing accelerator having an alkylurea group from the viewpoint of improving storage stability. Examples of the alkylurea-based curing accelerator having an alkylurea group include aromatic alkylureas and aliphatic alkylureas. Commercially available products of the alkylurea curing accelerator include, for example, U-CAT3512T (trade name, manufactured by San Afro Co., Ltd., aromatic dimethylurea) and U-CAT3513N (trade name, manufactured by San Afro Co., Ltd., aliphatic dimethylurea). . Among these, aromatic alkyl urea is preferable from the viewpoint of having an appropriately low cleavage temperature and easily curing the compound efficiently.

The blending amount of the curing accelerator may be any amount from which a curing accelerating effect is obtained, and is not particularly limited. However, from the viewpoint of improving the curability and fluidity of the resin composition at the time of moisture absorption, the compounding amount of the curing accelerator is preferably 0.1 part by mass or more and 30 parts by mass or less, more preferably 1 part by mass, based on 100 parts by mass of the epoxy resin. It may be more than 15 parts by mass or less. It is preferable that content of a hardening accelerator is 0.001 mass part or more and 5 mass parts or less with respect to 100 mass parts of the total mass of an epoxy resin and a phenol resin. When the blending amount of the curing accelerator is less than 0.1 parts by mass, it is difficult to obtain sufficient curing accelerating effect. When the blending amount of the curing accelerator exceeds 30 parts by mass, the storage stability of the compound tends to decrease. However, even if the blending amount and content of the curing accelerator are out of the above ranges, the effects relating to the present invention are obtained.

The coupling agent improves the adhesion between the resin composition and the metal element-containing particles constituting the metal powder, and improves the flexibility and mechanical strength of a molded body formed from the compound. The coupling agent may be, for example, at least one selected from the group consisting of silane-based compounds (silane coupling agents), titanium-based compounds, aluminum compounds (aluminum chelates), and aluminum/zirconium-based compounds. Silane coupling agents include, for example, epoxysilane, mercaptosilane, aminosilane, alkylsilane, ureidosilane, acid anhydride-based silane, vinylsilane and (meth)acryloyloxysilane At least 1 type selected from the group which consists of may be sufficient. The resin composition may contain one type of coupling agent among the above, and may contain a plurality of types of coupling agents among the above.

The resin composition may contain a compound having a siloxane bond (siloxane compound) in that the molding shrinkage rate of the compound is easily reduced and the heat resistance and withstand voltage property of the molded product are easily improved. A siloxane bond is a bond containing two silicon atoms (Si) and one oxygen atom (O), and may be expressed as -Si-O-Si-. The compound having a siloxane bond may be a polysiloxane compound.

For environmental safety, recyclability, molding processability and low cost of the compound, the compound may contain a flame retardant. The flame retardant is, for example, at least selected from the group consisting of bromine-based flame retardants, phosphorus-based flame retardants, hydrated metal compound-based flame retardants, silicon-based flame retardants, nitrogen-containing compounds, hindered amine compounds, organometallic compounds, and aromatic engineering plastics. It may be 1 paper. The resin composition may contain one kind of flame retardant among the above, and may contain a plurality of kinds of flame retardants among the above.

When forming a molded object from a compound using a mold, the resin composition may contain a release agent. The release agent also functions as an agent that improves the fluidity of the compound in molding (for example, transfer molding). Examples of the release agent include fatty acids such as higher fatty acids, fatty acid esters, and fatty acid metal salts.

Examples of release agents include fatty acids such as montanic acid, stearic acid, 12-oxystearic acid, and lauric acid, or esters thereof (eg, alkyl esters); fatty acid salts such as zinc stearate, calcium stearate, barium stearate, aluminum stearate, magnesium stearate, calcium laurate, zinc linoleate, calcium ricinoleate, and zinc 2-ethylhexanoate; Stearic acid amide, oleic acid amide, erucic acid amide, behenic acid amide, palmitic acid amide, lauric acid amide, hydroxystearic acid amide, methylenebisstearic acid amide, ethylenebisstearic acid amide, ethylenebislauric acid amide , distearyladipic acid amide, ethylenebisoleic acid amide, dioleyladipic acid amide, N-stearylstearic acid amide, N-oleylstearic acid amide, N-stearyl erucic acid amide, methylolstearic acid fatty acid amides such as amide and methylolbehenic acid amide; alcohols such as ethylene glycol and stearyl alcohol; Polyethers consisting of polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and modified products thereof; fluorine compounds such as fluorine-based oil, fluorine-based grease, and fluorine-containing resin powder; and waxes such as paraffin wax, polyethylene wax, amide wax, polypropylene wax, ester wax, carnauba, and microwax.

(metal powder)

Metal powder (metal element-containing particle|grains) may contain at least 1 sort(s) selected from the group which consists of a simple metal, an alloy, and a metal compound, for example. Metal powder may consist of at least 1 sort(s) chosen from the group which consists of a simple metal, an alloy, and a metal compound, for example. The alloy may also contain at least one selected from the group consisting of a solid solution, a eutectic, and an intermetallic compound. The alloy may be, for example, stainless steel (Fe-Cr-based alloy, Fe-Ni-Cr-based alloy, etc.). The metal compound may be an oxide such as ferrite, for example. The metal powder may also contain one type of metal element or multiple types 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. A compound may contain 1 type of metal powder, and may also contain multiple types of metal powder from which a composition differs.

Metal powder is not limited to said composition. The metal element contained in the metal powder is, for example, 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), Praseodymium (Pr), Neodymium (Nd), Samarium (Sm) and at least one selected from the group consisting of dysprosium (Dy). The metal powder may further contain elements other than the metal element. The metal powder may also contain, for example, carbon (C), oxygen (O), 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. Metal powder, for example, Fe-Si-based alloy, Fe-Si-Al-based alloy (Sendust), Fe-Ni-based alloy (Permalloy), Fe-Cu-Ni-based alloy (Permalloy), Fe-Co-based alloy (fermendule), Fe-Cr-Si alloy (electronic stainless steel), Nd-Fe-B alloy (rare earth magnet), Sm-Fe-N alloy (rare earth magnet), Al-Ni-Co alloy ( Alnico magnet) and a magnetic powder composed of at least one member selected from the group consisting of ferrite. 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 elements and compositions described above, or may contain plural kinds of elements and compositions described above.

The metal powder may be Fe alone. The metal powder may be an alloy (Fe-based alloy) containing iron. The Fe-based alloy may be, for example, a Fe-Si-Cr-based alloy or a Nd-Fe-B-based alloy. The metal 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 simple substance and Fe-based alloy, it is easy to produce a molded article having a high space factor and excellent magnetic properties from a compound. The metal powder may be Fe amorphous alloy.

Commercially available Fe amorphous alloy powders include, for example, AW2-08, KUAMET-6B2, 9A4-II (above, trade names manufactured by Epson Atomics Co., Ltd.), DAP MS3, DAP MS7, DAP MSA10, DAP PB, DAP PC, At least one selected from the group consisting of DAP MKV49, DAP 410L, DAP 430L, DAP HYB series (above, product name of Daido Tokushuko Co., Ltd.), MH45D, MH28D, MH25D, and MH20D (above, product name of Kobe Seiko Co., Ltd.) Paper may be used.

A compound is manufactured by mixing metal powder and a resin composition (each component which comprises a resin composition) heating. For example, you may knead with a kneader, a roll, a stirrer, etc., heating metal powder and a resin composition. By heating and mixing the metal powder and the resin composition, the resin composition adheres to a part or all of the surface of the metal element-containing particles constituting the metal powder to coat the metal element-containing particles, so that part or all of the epoxy resin in the resin composition is radiused. become a cargo As a result, a compound is obtained. 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 wax may be mixed in advance.

In kneading, you may knead metal powder, an epoxy resin, a hardening|curing agent, a dispersing agent, a hardening accelerator, and a coupling agent in a tank. After the metal powder, the dispersant, and the coupling agent are introduced into the tank and mixed, the epoxy resin, the curing agent, and the curing accelerator may be introduced into the tank and the raw materials in the tank may be kneaded. After kneading metal powder, a dispersing agent, an epoxy resin, a curing agent, and a coupling agent in a tank, a hardening accelerator may be put into the tank and raw materials in the tank may be further kneaded. A mixture (resin mixture) of an epoxy resin, a curing agent, a curing accelerator, and a dispersant is prepared in advance, and then a metal powder and a coupling agent are kneaded to prepare a metal mixture, and then the metal mixture and the above resin mixture may be kneaded. . What is necessary is just to mix|blend at the same timing as a dispersing agent, when using a release agent. What is necessary is just to mix|blend at the same timing as a coupling agent, when using a siloxane compound.

The kneading time varies depending on the type of kneading machine, the volume of the kneading machine, and the amount of compound produced, but is, for example, preferably 1 minute or longer, more preferably 2 minutes or longer, and even more preferably 3 minutes or longer. Further, the kneading time is preferably 20 minutes or less, more preferably 15 minutes or less, and still more preferably 10 minutes or less. When the kneading time is less than 1 minute, the kneading is insufficient, the moldability of the compound is impaired, and unevenness in the degree of curing of the compound is likely to occur. When the kneading time exceeds 20 minutes, for example, curing of the resin composition (for example, an epoxy resin and a curing agent) proceeds in the bath, and the fluidity and moldability of the compound are likely to be impaired. When kneading with a kneader while heating the raw material in the tank, the heating temperature is such that, for example, a semi-cured product of an epoxy resin (Epoxy resin of the B stage) is generated, and a cured product of the epoxy resin (Epoxy resin of the C stage) Any temperature at which the production is suppressed is sufficient. The heating temperature may be a temperature 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 still more preferably 70°C or higher. The heating temperature is preferably 150°C or lower, more preferably 120°C or lower, and still more preferably 110°C or lower. When the heating temperature is within the above range, the resin composition in the bath is softened to easily coat the surface of the metal element-containing particles constituting the metal powder, the semi-cured product of the epoxy resin is easily formed, and the complete curing of the epoxy resin during kneading is achieved. easy to be suppressed

[Moulded product and cured product]

The molded object according to this embodiment may be provided with the above compound. The cured product according to the present embodiment is formed by curing the above compound, and may be included in the above molded body. 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 article according to this embodiment may be used as a sealing material for electronic components or electronic circuit boards. As a result, cracks in the molded body caused by a difference in coefficient of thermal expansion between the metal member of the electronic component or the electronic circuit board and the molded body (sealing material) can be suppressed.

The molded body is manufactured by a manufacturing method including a step of pressurizing a compound in a mold. The method for producing a molded body may include a step of pressurizing a compound that covers part or all of the surface of a metal member in a mold. The method for producing a molded body may include only a step of pressurizing a compound in a mold, or may include other steps in addition to the step. The manufacturing method of a molded object may include a 1st process, a 2nd process, and a 3rd process. Below, the detail of each process is demonstrated.

In the first step, a compound is produced by the method described above.

In the second step, a molded body (B-stage molded body) is obtained by pressurizing the compound within the mold. In the second step, a molded body (B-stage molded body) may be obtained by pressing a compound that covers part or all of the surface of the metal member within the mold. In the second step, the resin composition is filled between the individual metal element-containing particles constituting the metal powder. And the resin composition functions as a binder (binder) to bind the metal element-containing particles to each other.

As the second step, transfer molding of the compound may be performed. In transfer molding, the compound may be pressurized at 3 MPa or more and 50 MPa or less. The higher the molding pressure, the easier it is to obtain a molded product with excellent mechanical strength. In consideration of 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 body formed by transfer molding is preferably 75% or more and 86% or less, more preferably 80% or more and 86% or less of the true density of the compound. When the density of the molded article is 75% or more and 86% or less, a molded article having excellent mechanical strength is easy to be obtained. Transfer molding WHEREIN: You may carry out a 2nd process and a 3rd process collectively.

In the third step, the molded body is cured by heat treatment to obtain a C-stage molded body. The temperature of the heat treatment may be any 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, more preferably 110°C or higher and 250°C or lower. In order to suppress oxidation of the metal powder in the molded body, 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 material deteriorates due to a small amount of oxygen inevitably contained in the heat treatment atmosphere. In order to sufficiently cure the resin composition while suppressing oxidation of the metal powder and deterioration of the cured resin product, the holding time of the heat treatment temperature is 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 more detail by examples and comparative examples, but the present invention is by no means limited by these examples.

Details of each component used to prepare 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)

Trifunctional type epoxy resin (trade name: VG3101L, epoxy equivalent: 212 g/eq, manufactured by PRINTEC Co., Ltd.)

(curing agent)

Triphenylmethane type phenolic resin (trade name: MEHC-7500-3S, hydroxyl equivalent: 103 g/eq, manufactured by Maywa Kasei Co., Ltd.)

- Biphenylene aralkyl type phenolic resin (trade name: MEHC-7851SS manufactured by Maywa Kasei Co., Ltd., hydroxyl equivalent: 202 g/eq)

(curing accelerator)

・Imidazole-based curing accelerator (trade name: 2E4MZ manufactured by Shikoku Kasei Kogyo Co., Ltd.)

(coupling agent)

・Methacryloxyoctyltrimethoxysilane (trade name: KBM-5803 manufactured by Shin-Etsu Chemical Industry Co., Ltd.)

3-glycidoxypropyltriethoxysilane (trade name: KBM-403 manufactured by Shin-Etsu Chemical Industry Co., Ltd.)

(siloxane compound)

・Caprolactone-modified dimethylsilicone (trade name: DBL-C32 manufactured by Gelest Co., Ltd.)

(dispersant)

The following phosphoric acid esters having a group represented by "-OR"

Phosphate ester in which R is an organic group having 4 carbon atoms (trade name: JP-504 manufactured by Johoku Chemical Industry Co., Ltd.)

Phosphate ester in which R is an organic group having 6 carbon atoms (trade name: JP-506H manufactured by Johoku Chemical Industry Co., Ltd.)

Phosphate ester in which R is an organic group having 8 carbon atoms (trade name: JP-508 manufactured by Johoku Chemical Industry Co., Ltd.)

Phosphate ester in which R is an organic group having 13 carbon atoms (trade name: JP-513 manufactured by Johoku Chemical Industry Co., Ltd.)

(release agent)

・Partially saponified montanic acid ester wax (trade name: LICOWAX-OP, manufactured by Clariant Chemicals Co., Ltd.)

・Zinc stearate (trade name: zinc stearate manufactured by Nichiyu Co., Ltd.)

(metal powder)

・Amorphous iron powder (trade name: 9A4-II manufactured by Epson Atomics Co., Ltd., average particle diameter 24 μm)

・Amorphous iron powder (trade name: AW2-08 manufactured by Epson Atomics Co., Ltd., average particle size: 5.3 μm)

[Preparation of compound]

(Example)

The epoxy resin, curing agent, curing accelerator, dispersing agent, and release agent shown in Table 1 were charged into a poly container in the compounding amounts (unit: g) shown in the same table. A resin mixture was prepared by mixing these materials in a poly container for 10 minutes. The resin mixture corresponds to all other components except for the coupling agent and siloxane compound in the resin composition.

Two types of amorphous iron powders shown in Table 1 were uniformly mixed for 5 minutes with a pressurized twin shaft kneader (manufactured by Nippon Spindle Seizo Co., Ltd., capacity 5 L) to prepare metal powder. The coupling agents and siloxane compounds shown in Table 1 were added to the metal powder in the biaxial 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 material obtained by the above melting and kneading to room temperature, the kneaded material was pulverized with a hammer until the kneaded material had a predetermined particle size. In addition, the above "melting" means melting of 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 in the preparation process of the compound. By the above method, the compound of the Example was prepared.

(Comparative example)

Compounds of comparative examples were prepared in the same manner as in Examples except that the blending amount of the metal powder was changed as shown in Table 1 without using a dispersant.

[Evaluation of compound]

The following evaluation was performed about the compound obtained by the Example and the comparative example. The results are shown in Table 1.

(flow characteristics: 140°C minimum melt viscosity)

As follows, the lowest melt viscosity (unit: Pa·s) of the compound at 140°C was measured. As a measuring device, CFT-100 (flow tester) manufactured by Shimadzu Corporation was used. As a sample for measurement, a tablet was produced with a 7 g compound. The fluidity of the compound was evaluated under conditions of 140°C, residual heat for 20 seconds, and a load of 100 kg. The press-in distance (unit: mm) of the plunger until the flow of the compound stopped was measured as a flow tester stroke. The time until the flow of the compound stopped was measured as the flow time. These measured values were used as an index of fluidity.

(flow characteristics: 140 ℃ disk flow)

As a sample for measurement, 5 g of compound (powder) was used. The compound was placed on the flat surface of the lower mold. While pressing the flat upper mold against the compound, the compound was sandwiched between the upper mold and the lower mold. By compressing the compound between the upper mold and the lower mold for 360 seconds under a load of 8 kg, a substantially disk-shaped molded body made of the compound was formed. The temperature of the compound during compression was maintained at 140°C. The largest and smallest diameters of the disc-shaped molded article were measured. The average value of the major axis and the minor axis corresponds to the disk flow (unit: mm).

[Table 1]

Claims (7)

Including a resin composition containing a metal powder, an epoxy resin, a curing agent and a dispersing agent,
The content of the metal powder is 90% by mass or more and 98% by mass or less,
The compound in which the said dispersing agent contains a phosphate ester. The method of claim 1,
A compound in which the phosphoric acid ester has a group represented by -OR (R represents an organic group having 4 or more carbon atoms). The method of claim 2,
The compound wherein the organic group is an alkyl group having 4 or more carbon atoms or a group in which an ether bond is inserted into at least a part of the carbon-carbon bonds in the alkyl group having 4 or more carbon atoms. The method of claim 3,
A compound wherein the alkyl group and the group in which an ether bond is inserted into at least a part of the carbon-carbon bonds in the alkyl group have a substituent. The method according to any one of claims 1 to 4,
A compound in which the content of the dispersant is 1 part by mass or less with respect to 100 parts by mass of the metal powder. A molded body comprising the compound according to any one of claims 1 to 5. A cured product of the compound according to any one of claims 1 to 5.