TW202214784A - Compound, molded body and cured product - Google Patents

Abstract

This compound contains at least a metal powder and a resin composition; the resin composition contains at least an epoxy resin and a phosphoric acid ester; and the content of the epoxy resin in the compound is from 1.0% by mass to 2.0% by mass.

Description

Compounds, shaped bodies and cured products

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

A composite containing metal powder and a thermosetting resin is used as a raw material for various industrial products such as inductors depending on the various physical properties of the metal powder (see Patent Documents 1 and 2 below).

[Patent Document 1] Japanese Patent Laid-Open No. 2011-211026 [Patent Document 2] Japanese Patent Laid-Open No. 2017-133071

When manufacturing an industrial product from a compound, the compound is supplied and filled into the mold through the flow path, or parts such as coils are embedded in the compound in the mold. During these steps, the fluidity of the complex is required. When the compound does not have sufficient fluidity, it is difficult to uniformly fill the compound into the mold, and voids are likely to be formed in the molded body formed of the compound. The fluidity of the composite increases as the content of metal powder in the composite decreases.

On the other hand, in order to improve the magnetic properties of the composite used for an inductor or the like, it is preferable that the content (filling ratio) of the metal powder in the composite be high. For example, the values of the magnetic properties of the composite, such as relative permeability and saturation magnetic flux density, increase as the content of the metal powder in the composite increases. However, as the content of metal powder in the composite increases, the composite becomes difficult to flow.

The present invention has been made in view of the above-mentioned problems, and an object of one aspect of the present invention is to provide a composite having excellent fluidity, a molded body containing the composite, and a cured product of the composite.

The composite of one aspect of the present invention contains at least a metal powder and a resin composition, the resin composition contains at least an epoxy resin and a phosphoric acid ester, and the content of the epoxy resin in the composite is 1.0 mass % or more and 2.0 mass % or less.

The ratio of the phosphate ester to 100 parts by mass of the metal powder may be 0.01 part by mass or more and 0.05 part by mass or less.

The melt viscosity of the composite at 140° C. may be 10 Pa·s or more and 1500 Pa·s or less.

The content of the metal powder in the composite may be 90% by mass or more and 98% by mass or less.

The composite of one embodiment of the present invention can be used for at least one of transfer molding and compression molding.

A molded body of one embodiment of the present invention contains the above-mentioned composite.

A cured product of one embodiment of the present invention is a cured product of the above-mentioned composite. [Inventive effect]

According to one aspect of the present invention, a composite having excellent fluidity, a molded body comprising the composite, and a cured product of the composite are provided.

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

＜Summary of the complex＞ The composite of this embodiment contains at least a metal powder and a resin composition. That is, the composite may be a mixture of metal powder and resin composition. The composite can be referred to as a magnetic seal.

The metal powder is composed of a plurality of metal particles. The metal powder may contain, for example, at least one selected from the group consisting of a metal element (pure metal), an alloy, an amorphous powder, and a metal compound. The metal powder may be referred to as a filler formed of metal.

The resin composition contains at least an epoxy resin and a phosphoric acid ester.

The epoxy resin melts at a temperature below the curing temperature, whereby the fluidity of the composite is improved. And the epoxy resin bonds the metal powders to each other by thermal curing. Furthermore, the epoxy resin electrically insulates the metal powders from each other. Content of the epoxy resin in a composite is 1.0 mass % or more and 2.0 mass % or less. When the content of the epoxy resin in the composite is within the above range, and the composite contains phosphoric acid ester, the composite can have high fluidity (low melt viscosity). When the content of the epoxy resin in the composite is less than the lower limit value, it is difficult for the composite to have high fluidity. When the content of the epoxy resin in the composite is within the above range, and the composite does not contain phosphate ester, it is also difficult for the composite to have high fluidity. When the content of the epoxy resin in the composite is larger than the upper limit value, it is difficult to manufacture the composite. Since the composite tends to have high fluidity, the content of the epoxy resin in the composite may be 1.86 mass % or more and 1.90 mass % or less. In other words, the ratio of the epoxy resin to 100 parts by mass of the metal powder may be 1.92 parts by mass or more and 1.97 parts by mass or less.

Phosphate esters can be represented, for example, as OP(OR ¹ )(OR ² )(OR ³ ). R ¹ , R ² and R ³ are each hydrogen or an arbitrary hydrocarbon group, and at least one of R ¹ , R ² and R ³ is a hydrocarbon group. The hydrocarbyl group can be, for example, an alkyl group or an aryl group. Phosphates are compounds different from phosphites. Phosphite can be represented as P(OR ¹ )(OR ² )(OR ³ ), for example. The resin composition may contain phosphite in addition to phosphoric acid ester. However, it is difficult to have a high fluidity in the compound containing no phosphate and phosphite as compared with the compound of the present embodiment. In addition to the phosphate ester, the resin composition may contain other dispersants (eg, coupling agents).

Phosphate esters can be dispersants. Since the phosphoric acid group of the phosphoric acid ester has polarity, it is easy to be selectively adsorbed on the surface of the metal particle. On the other hand, since the hydrocarbon group of the phosphate ester has lipophilicity, the resin composition containing the epoxy resin easily exists between the metal particles to which the phosphate ester is adsorbed. Therefore, aggregation of the metal powder is suppressed due to the phosphate ester, and each metal particle is easily dispersed in the composite. In other words, due to the phosphoric acid ester, it is difficult for the metal particles to directly contact each other, and the direct friction between the metal particles is easily suppressed, and the friction between the metal particles and the resin composition is also easily suppressed. As described above, when the phosphate ester acts as a dispersant on the metal powder, the fluidity of the composite is improved. For example, by the compound containing phosphate ester, the melt viscosity of the compound is reduced. The fluidity of the compound containing the phosphate ester tends to be superior to that of the compound containing the dispersant other than the phosphate ester. The direct friction between the metal particles can be evaluated based on the torque value measured by the gel time measuring device. The more the direct friction between the metal particles is suppressed, the more the torque value decreases. As an apparatus for measuring the gel time, CURELASTOMETER manufactured by JSR Corporation can be used.

The melt viscosity of the composite at 140° C. may be 10 Pa·s or more and 1500 Pa·s or less, and preferably 401 Pa·s or more and 650 Pa·s or less. When the content of the epoxy resin in the composite is within the above range, and the composite contains phosphoric acid ester, the composite can have a low melt viscosity (high fluidity) as described above. When the melt viscosity of the compound is within the above-mentioned range, the molten compound can be easily filled into the mold uniformly, and defects (voids, burrs, etc.) in the molded body and cured product formed of the compound are easily suppressed. Therefore, compounds with a low melt viscosity as described above are suitable for transfer molding.

The ratio of the phosphate ester to 100 parts by mass of the metal powder may be 0.01 part by mass or more and 0.05 part by mass or less. When the ratio of the phosphate ester is 0.01 part by mass (preferably 0.02 part by mass) or more, high fluidity (low melt viscosity) of the compound due to the phosphate ester is easily obtained. Phosphate esters can hinder the curing of epoxy resins. However, when the ratio of the phosphoric acid ester is 0.05 parts by mass or less, the inhibition of curing of the epoxy resin by the phosphoric acid ester is easily suppressed. In other words, when the ratio of the phosphate ester is 0.05 parts by mass or less, the gelation time (curing time) of the composite is shortened. For the same reason, the ratio of the phosphate ester to 100 parts by mass of the metal powder may be 0.02 parts by mass or more and 0.03 parts by mass or less.

The content of the metal powder in the composite may be 90% by mass or more and 98% by mass or less, or 96% by mass or more and 97.5% by mass or less. As the content (filling ratio) of the metal powder in the composite increases, the relative magnetic permeability and saturation magnetic flux density of the composite tend to increase. A compound having high relative magnetic permeability and high saturation magnetic flux density is suitable, for example, as a raw material for an inductor seal or a magnetic core of an inductor. However, as the content of metal powder in the composite increases, the composite becomes difficult to flow. Assuming that the content of the metal powder in the phosphate-free composite is 90% by mass or more, the melt viscosity of the composite is significantly increased. However, even when the content of the metal powder in the composite is 90 mass % or more, the composite of the present embodiment can have high fluidity (low melt viscosity) because the composite contains epoxy resin and phosphate ester. When the content of the metal powder in the composite is equal to or less than the above-mentioned upper limit value, high fluidity (low melt viscosity) due to epoxy resin and phosphoric acid ester is easily obtained.

<Details of the composition of the complex> (resin composition) The resin composition may be a component containing an epoxy resin and a phosphoric acid ester, and may be the remaining components (non-volatile components) of all the components constituting the composite excluding the metal powder and the organic solvent. That is, the resin composition may contain other components in addition to the epoxy resin and the phosphoric acid ester. For example, the resin composition may further contain a curing agent. The resin composition may further contain a curing accelerator. The resin composition may further contain wax (release agent). The resin composition may further contain additives. The additive may be, for example, a coupling agent, a flame retardant, or the like.

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

The resin composition may be attached to the surface of each metal particle constituting the metal powder. The resin composition may cover a part of the surface of each metal particle, or may cover the entire surface of each metal particle. The composite may contain metal powder and an uncured resin composition. The composite may contain metal powder and a semi-cured resin composition (eg, a B-stage resin composition). The composite may contain both an uncured resin composition and a semi-cured resin composition. The composite can be a powder. The composite can also be an ingot. The composite can also be a paste.

The content of the resin composition in the composite may be, for example, 2 mass % or more and 10 mass % or less.

[Phosphate] The resin composition may contain a phosphoric acid ester. The resin composition may contain a plurality of phosphoric acid esters. The phosphoric acid ester contained in the resin composition may be at least one phosphoric acid ester selected from the group consisting of phosphoric acid monoester, phosphoric acid diester, and phosphoric acid triester.

The phosphoric acid ester contained in the resin composition may be selected from phosphoric acid ester salts of acid group-containing copolymers, compound 1 represented by the following chemical formula 1, compound 2 represented by the following chemical formula 2, and represented by the following chemical formula 3. at least one phosphoric acid ester in the group consisting of compound 3 represented by the following chemical formula 4 and compound 4 represented by the following chemical formula 4. When at least one of these phosphoric acid esters is contained in the resin composition, the composite tends to have high fluidity. In particular, when the phosphate ester salt of the acid group-containing copolymer is contained in the resin composition, the composite tends to have high fluidity. The phosphoric acid ester salt of the acid group-containing copolymer can be, for example, disperbyk-111 (trade name) manufactured by BYK-Chemie GmbH. The acid value of the phosphate ester salt of the acid group-containing copolymer may be 129. Disperbyk-111 has an acid value of 129. The compound 1 represented by the following chemical formula 1 can be, for example, JP-504 manufactured by JOHOKU CHEMICAL CO., LTD. The compound 2 represented by the following chemical formula 2 may be, for example, JP-506H manufactured by JOHOKU CHEMICAL CO., LTD. The compound 3 represented by the following chemical formula 3 may be, for example, JP-508 manufactured by JOHOKU CHEMICAL CO., LTD. The compound 4 represented by the following chemical formula 4 can be, for example, JP-513 manufactured by JOHOKU CHEMICAL CO., LTD. (C ₄ H ₉ O) _n OP(OH) _3-n (1) n in the above Chemical Formula 1 may be 1 or 2. n in the above chemical formula 1 may be 1 or more and 3 or less. (C ₄ H ₉ OCH ₂ CH ₂ O) _n OP(OH) _3-n (2) n in the above Chemical Formula 2 may be 1 or 2. n in the above chemical 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) n in the above Chemical Formula 3 may be 1 or 2. n in the above chemical formula 3 may be 1 or more and 3 or less. (isо-C ₁₃ H ₂₇ O) _n OP(OH) _3-n (4) n in the above Chemical Formula 4 may be 1 or 2. n in the above Chemical Formula 4 may be 1 or more and 3 or less.

[Epoxy resin] The resin composition contains at least an epoxy resin as a thermosetting resin. When the composite contains an epoxy resin which is relatively excellent in fluidity among thermosetting resins, the fluidity, filling property, storage stability and moldability of the composite are improved. However, as long as the effects of the present invention are not inhibited, the composite may contain other resins in addition to the epoxy resin. For example, the resin composition may contain at least one of a phenol resin and a polyamide imide resin as a thermosetting resin. When the resin composition contains both an epoxy resin and a phenol resin, the phenol resin can also function as a curing agent for the epoxy resin. In addition to the thermosetting resin, the resin composition may contain a thermoplastic resin. The thermoplastic resin may be, for example, at least one selected from the group consisting of acrylic resin, polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyethylene terephthalate, and rubber (elastomer). The resin composition may also contain a silicone resin.

The epoxy resin may be, for example, a resin having two or more epoxy groups in one molecule. For example, the epoxy resin can be selected from biphenyl type epoxy resin, biphenyl aralkyl type epoxy resin, biphenyl aralkyl type epoxy resin, stilbene type epoxy resin, diphenyl epoxy resin Methane type epoxy resin, sulfur atom-containing epoxy resin, novolac type epoxy resin, dicyclopentadiene type epoxy resin, salicylic resin type epoxy resin, copolymerization type epoxy resin of naphthol type and phenol type , epoxides of aralkyl-type phenol resins, bisphenol-type epoxy resins, epoxy resins containing bisphenol skeleton, glycidyl ether-type epoxy resins of alcohols, modified stubble and/or stubble Glycidyl ether type epoxy resin of phenol 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 Resin, glycidyl ether type epoxy resin containing naphthalene ring-containing phenol resin, glycidyl ester type epoxy resin, glycidyl type or methyl glycidyl type epoxy resin, alicyclic epoxy resin, halogenated phenol novolak type Epoxy resin, o-cresol novolac type epoxy resin, hydroquinone type epoxy resin, trimethylpropane type epoxy resin and linear aliphatic epoxy resin obtained by oxidizing olefin bond with peracid such as peracetic acid at least one of the group consisting of.

The epoxy resin may be selected from the group consisting of biphenyl-type epoxy resins, o-cresol novolak-type epoxy resins, phenol novolak-type epoxy resins, bisphenol-type epoxy resins, and bisphenol-containing epoxy resins from the viewpoint of excellent fluidity. At least one of the group consisting of epoxy resin of skeleton, salicylic novolac type epoxy resin and naphthol novolac 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 be selected from the group consisting of, for example, a hydroquinone-type epoxy resin, a bisphenol-type epoxy resin, a sulfide-type epoxy resin, and a biphenyl-type epoxy resin. at least one of them. A commercially available crystalline epoxy resin can be selected from, for example, EPICLON 860, EPICLON 1050, EPICLON 1055, EPICLON 2050, EPICLON 3050, EPICLON 4050, EPICLON 7050, EPICLON HM-091, EPICLON HM-101, EPICLON N-730A , EPICLON N-740, EPICLON N-770, EPICLON N-775, EPICLON N-865, EPICLON HP-4032D, EPICLON HP-7200L, EPICLON HP-7200, EPICLON HP-7200H, EPICLON HP-7200HH, EPICLON HP-7200HHH , EPICLON HP-4700, EPICLON HP-4710, EPICLON HP-4770, EPICLON HP-5000, EPICLON HP-6000, N500P-2 and N500P-10 (the above are trade names manufactured by DIC Corporation), NC-3000, NC- 3000-L, NC-3000-H, NC-3100, CER-3000-L, NC-2000-L, XD-1000, NC-7000-L, NC-7300-L, EPPN-501H, EPPN-501HY, EPPN-502H, EOCN-1020, EOCN-102S, EOCN-103S, EOCN-104S, CER-1020, EPPN-201, BREN-S, BREN-10S (the above are trade names manufactured by Nippon Kayaku Co., Ltd.) , at least one of the group consisting of YX-4000, YX-4000H, YL4121H and YX-8800 (the above are trade names manufactured by Mitsubishi Chemical Corporation).

The resin composition may contain an isocyanate-modified epoxy resin as the epoxy resin from the viewpoint that the molding shrinkage rate of the composite is easily reduced. As a commercial item of an isocyanate-modified epoxy resin, AER-4001 by Asahi Kasei Corporation (former Asahi Kasei E-Materials Corporation) can be used, for example.

The resin composition may contain one of the above epoxy resins. The resin composition may contain plural types of epoxy resins described above.

[Hardener] The curing agent is classified into a curing agent that cures epoxy resins in a range from a low temperature to room temperature, and a curing agent of a heat curing type that cures epoxy resins with heating. Examples of curing agents for curing epoxy resins in the range from low temperature to room temperature are aliphatic polyamines, polyamidoamines, and polythiols. The heat-curable curing agent is, for example, aromatic polyamines, acid anhydrides, phenol novolac resins, dicyandiamine (DICY), and the like.

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

The phenol resin may be, for example, a copolymer-type phenol resin selected from aralkyl-type phenol resins, dicyclopentadiene-type phenol resins, salicylic phenol resins, novolak-type phenol resins, benzaldehyde-type phenols, and aralkyl-type phenols , stubble and/or stubble modified phenol resin, melamine modified phenol resin, terpene modified phenol resin, dicyclopentadiene type naphthol resin, cyclopentadiene modified phenol resin, polycyclic aromatic At least one of the group consisting of a ring-modified phenol resin, a biphenyl-type phenol resin, and a triphenylmethane-type phenol resin. The phenol resin may be a copolymer composed of two or more of the above.

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. Phenols constituting the phenol novolak resin may be selected from the group consisting of, for example, phenol, cresol, xylenol, resorcinol, catechol, bisphenol A, bisphenol F, phenylphenol, and aminophenol. at least one of them. The naphthols constituting the phenol novolak resin may be, 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 be, for example, at least one selected from the group consisting of formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde, and salialdehyde.

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 be, for example, at least one selected from the group consisting of resorcinol, catechol, bisphenol A, bisphenol F, and substituted or unsubstituted biphenols .

The resin composition may contain one of the above-mentioned phenol resins. The resin composition may contain plural types of the above-mentioned phenol resins. The resin composition may contain one of the above-mentioned curing agents. The resin composition may contain plural kinds of curing agents described above.

The ratio of the active group (phenolic OH group) in the curing agent that reacts with the epoxy group in the epoxy resin can be preferably 0.5 to 1.5 equivalents relative to 1 equivalent of the epoxy group in the epoxy resin, and more Preferably it is 0.6-1.4 equivalent, More preferably, it is 0.8-1.2 equivalent. When the ratio of active groups in the curing agent is less than 0.5 equivalent, it is difficult to obtain a sufficient modulus of elasticity of the obtained cured product. On the other hand, when the ratio of the active group in the curing agent exceeds 1.5 equivalents, the mechanical strength after curing of the molded body formed of the composite tends to decrease.

[Curing accelerator] The curing accelerator is not limited, for example, as long as it reacts with the epoxy resin and accelerates the curing of the epoxy resin. The curing accelerator may be, for example, imidazoles such as alkyl-substituted imidazole or benzimidazole. The resin composition may contain a curing accelerator. The resin composition may contain a plurality of curing accelerators. When the resin composition contains a curing accelerator, the moldability and releasability of the composite are easily improved. In addition, by containing a curing accelerator in the resin composition, the mechanical strength of a molded body (eg, electronic part) produced using the composite is improved, or the storage stability of the composite in a high temperature and/or high humidity environment is improved. . As a commercial item of an imidazole-based curing accelerator, for example, a product selected from the group consisting of 2MZ-H, C11Z, C17Z, 1,2DMZ, 2E4MZ, 2PZ-PW, 2P4MZ, 1B2MZ, 1B2PZ, 2MZ-CN, C11Z-CN, 2E4MZ- can be used At least one of the group consisting of CN, 2PZ-CN, C11Z-CNS, 2P4MHZ, TPZ, and SFZ (the above are trade names manufactured by Shikoku Chemicals Corporation).

The compounding quantity of a hardening accelerator will not be specifically limited if it is an amount which can obtain a hardening-accelerating effect. However, from the viewpoint of improving the curability and fluidity at the time of moisture absorption of the resin composition, the blending amount of the curing accelerator may preferably be 0.1 parts by mass or more and 30 parts by mass with respect to 100 parts by mass of the epoxy resin. Below, it is more preferable that it is 1 mass part or more and 15 mass parts or less. The content of the curing accelerator is preferably 0.001 parts by mass or more and 5 parts by mass or less with respect to 100 parts by mass in total of the mass of the epoxy resin and the curing agent (eg, phenol resin). When the compounding amount of the curing accelerator is less than 0.1 part by mass, it is difficult to obtain a sufficient curing acceleration effect. When the compounding amount of the curing accelerator exceeds 30 parts by mass, the storage stability of the composite tends to decrease.

[Coupling Agent] The coupling agent improves the adhesiveness between the resin composition and the metal particles constituting the metal powder, and improves the flexibility and mechanical strength of the molded body formed of the composite. The coupling agent may be, for example, at least one selected from the group consisting of silane-based compounds (silane coupling agents), titanium-based compounds, aluminum compounds (aluminum chelate compounds), and aluminum/zirconium-based compounds. The silane coupling agent may be, for example, at least one selected from the group consisting of epoxysilane, mercaptosilane, aminosilane, alkylsilane, ureidosilane, acid anhydride silane, and vinylsilane. In particular, an aminophenyl silane coupling agent is preferable. The resin composition may contain one of the above-mentioned coupling agents, or may contain plural kinds of the above-mentioned coupling agents. Commercially available coupling agents, for example, can be selected from vinyltrimethoxysilane (KBM-1003), vinyltriethoxysilane (KBE-1003), 2-(3,4-epoxycyclohexyl)ethyltrimethyl Oxysilane (KBM-303), 3-glycidyloxypropylmethyldimethoxysilane (KBM-402), 3-glycidoxypropyltrimethoxysilane (KBM-403), p-benzene vinyltrimethoxysilane (KBM-1403), 3-methacryloyloxypropylmethyldimethoxysilane (KBM-502), 3-methacryloyloxypropyltrimethoxysilane ( KBM-503), 3-methacryloyloxypropylmethyldiethoxysilane (KBE-502), 3-methacryloyloxypropyltriethoxysilane (KBE-503), 3 - Acryloyloxypropyltrimethoxysilane (KBM-5103), N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane (KBM-602), N-2 -(Aminoethyl)-3-aminopropyltrimethoxysilane (KBM-603), 3-aminopropyltrimethoxysilane (KBM-903), 3-aminopropyltriethoxy Silane (KBE-903), 3-triethoxysilyl-N-(1,3-dimethyl-butylene)propylamine (KBE-9103), N-phenyl-3-aminopropyltrimethoxy Silane (KBM-573), N-vinylbenzyl-2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride (KBM-575), tris-(trimethoxymethylsilane) propyl) isocyanurate (KBM-9659), 3-ureidopropyl trialkoxysilane (KBE-585), 3-mercaptopropyl methyldimethoxysilane (KBM-802), 3-mercaptopropyltrimethoxysilane (KBM-803), 3-isocyanatopropyltriethoxysilane (KBM-9007), octenyltrimethoxysilane (KBM-1083), glycidyloxyoctyl Trimethoxysilane (KBM-4803), Methacryloyloxyoctyltrimethoxysilane (KBM-5803), Methyltrimethoxysilane (KBM-13), Methyltriethoxysilane (KBE- 13), dimethyldimethoxysilane (KBM-22), dimethyldiethoxysilane (KBE-22), phenyltrimethoxysilane (KBM-103), phenyltriethoxysilane (KBE-103), n-propyltrimethoxysilane (KBM-3033), n-propyltriethoxysilane (KBE-3033), hexyltriethoxysilane (KBM-3063), hexyltriethoxy Silane (KBE-3063), Octyltriethoxysilane (KBE-3083), Decyltrimethoxysilane (KBM-3103C), 1,6-(Trimethoxysilyl)hexane (KBM-3066) , trifluoropropyl trimethoxysilane (KBM-7103), hexamethyldisilazane (SZ-31) and hydrolyzable groups At least one of the group consisting of siloxane (KPN-3504) (the above is a trade name manufactured by Shin-Etsu Chemical Co., Ltd.). The coupling agent can also be a silicone alkoxy oligomer (silicone oligomer with an alkoxy group). The silicone alkoxy oligomer may have at least one alkoxy group among a methoxy group and an ethoxy group. The silicone alkoxy oligomer may have at least one organic substituent selected from the group consisting of epoxy, methyl, mercapto, acryl, methacrylo, vinyl, and phenyl. The silicone alkoxy oligomer can be selected from KR-517, X-41-1059A, X-24-9590, KR-516, X-41-1805, X-41-1818, X-41-1810, for example , KR-513, X-40-9296, KR-511, KC-89S, KR-515, KR-500, X-40-9225, X-40-9246, X-40-9250, KR-41N, X - At least one of the group consisting of 40-9227, KR-510, KR-9218 and KR-213 (the above are trade names manufactured by Shin-Etsu Chemical Co., Ltd.).

[wax] Waxes improve the fluidity of the compound during molding (eg, transfer molding) and function as a mold release agent. The wax may be at least any one of fatty acids such as higher fatty acids, fatty acid esters, and fatty acid salts.

For example, the wax may be selected from fatty acids such as montanic acid, stearic acid, 12-oxystearic acid, and lauric acid, or esters thereof, zinc stearate, calcium stearate, stearic acid, etc. Barium, aluminum stearate, magnesium stearate, zinc laurate, calcium laurate, zinc linoleate, calcium ricinoleate, zinc 2-ethylhexanoate and other fatty acid salts, amide stearate, amide oleate amine, erucamide, behenamide, palmitic acid amide, lauric acid amide, hydroxystearic acid amide, methylene bis-stearic acid amide, ethylene bis-stearic acid amide, Ethyl amide dilaurate, amide distearyl adipate, amide ethylene dioleate, amide dioleyl adipate, N-stearyl amide stearate, N -Oleyl stearic acid amide, N-stearyl erucamide, hydroxymethyl stearic acid amide, hydroxymethyl behenic acid amide and other fatty acid amides, fatty acids such as butyl stearate Alcohols such as esters, ethylene glycol, stearyl alcohol, polyethers including polyethylene glycol, polypropylene glycol, polytetramethylene glycol and their modifications, polysiloxanes such as silicone oil and silicone grease Fluorine compounds such as alkanes, fluorine-based oils, fluorine-based greases, and fluorine-containing resin powders, as well as paraffin wax, polyethylene wax, amide wax, polypropylene wax, ester wax, carnauba wax, and microcrystalline wax ( At least one of the group consisting of waxes such as micro wax.

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

(mineral powder) The metal powder may contain, for example, at least one selected from the group consisting of a single metal (pure metal) and an alloy. The metal powder may be composed of, for example, at least one selected from the group consisting of a metal element (pure metal), an alloy, an amorphous powder, and a metal compound. The alloy may contain at least one selected from the group consisting of solid solution, eutectic, and intermetallic. The alloy may be stainless steel (Fe-Cr-based alloy, Fe-Ni-Cr-based alloy, etc.), for example. The metal powder may contain one metal element or a plurality of metal elements. The metal element contained in the metal powder may be, for example, a base metal element, a noble metal element, a transition metal element or a rare earth element. The composite may contain one metal powder or a plurality of metal powders.

The metal element contained in the metal powder can be selected from iron (Fe), copper (Cu), titanium (Ti), manganese (Mn), cobalt (Co), nickel (Ni), zinc (Zn), aluminum ( Al), tin (Sn), chromium (Cr), barium (Ba), strontium (Sr), lead (Pb), silver (Ag), strontium (Pr), neodymium (Nd), samarium (Sm) and dysprosium ( At least one of the group consisting of Dy). The metal powder may contain elements other than metal elements. For example, the metal powder may contain oxygen (О), beryllium (Be), phosphorus (P), 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. For example, the metal powder may be selected from Fe-Si-based alloys, Fe-Si-Al-based alloys (Sendust), Fe-Ni-based alloys (Permalloy), Fe-Cu- Ni-based alloys (high magnetic permeability alloys), Fe-Co-based alloys (Permendur), Fe-Cr-Si-based alloys (electromagnetic stainless steel), Nd-Fe-B-based alloys (rare earth magnets), Sm - Magnetic powder composed of at least one of the group consisting of Fe-N-based alloys (rare earth magnets) and Al-Ni-Co-based alloys (Alnico magnets). 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 consist of only one element or constituent. The metal powder may also contain a plurality of elements or constituents.

The metal powder may also be Fe monomer (pure iron). The metal powder may be an alloy containing iron (Fe-based alloy). Fe-based alloys may be, for example, Fe-Si-Cr-based alloys, Nd-Fe-B-based alloys, or Sm-Fe-N-based alloys. 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 alone and an Fe-based alloy, it is easy to produce a molded body having a high space factor and excellent magnetic properties from the composite. The metal powder may also be an Fe amorphous alloy. As a commercial item of Fe amorphous alloy powder, for example, one selected from the group consisting of AW2-08, KUAMET-6B2 (the above are trade names manufactured by Epson Atmix Corporation), DAP MS3, DAP MS7, DAP MSA10, DAP PB, DAP PC, DAP MKV49, DAP 410L, DAP 430L, DAP HYB series (the above are the trade names made by Daido Steel Co., Ltd.), MH45D, MH28D, MH25D and MH20D (the above are the trade names made by Kobe Steel, Ltd.) at least one of the group.

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

＜Use of the complex＞ The composite can be used for at least one of transfer molding (transfer molding) and compression molding. Transfer molding is one of the injection molding methods of thermosetting resins. Transfer molding may be referred to as press feed molding. The transfer molding may include: a step of heating the compound in a heating chamber to fluidize it; a step of supplying (pressing) the fluidized compound from the heating chamber into the mold through a casting runner; and A step in which the compound in the mold is heated to cure it. The transfer molding can include: the step of heating the compound in a heating chamber to make it fluidized; supplying the fluidized compound powder from the heating chamber into the plunger, and supplying it from the plunger to the mold through the runner (press-in ) the step of compounding; and the step of heating and curing the compound in the mold. The pressure acting on the composite during transfer molding can be, for example, 3 MPa or more and 100 MPa or less. Since the compound of this embodiment exhibits excellent fluidity and filling properties by heating, it is easy to flow in a thin runner, and it is easy to uniformly fill the space (cavity) in the mold. Therefore, by processing the composite by transfer molding, a molded body and a cured product with few defects such as voids and burrs can be produced. The composite molding method can also be compression molding.

Depending on the composition or combination of the metal powder contained in the composite, various properties (for example, electromagnetic properties or magnetic properties) of each of the molded body and the cured product formed from the composite can be freely controlled. Therefore, the molded body and the cured product can be used for various industrial products or their raw materials. The molded body formed from the composite may contain at least any one of an uncured resin composition and a B-stage resin composition (semi-cured resin composition). The shaped body can consist only of the composite. The cured product of the composite or molded body may contain the C-stage resin composition (cured product of the resin composition).

Industrial products manufactured using the composite may be, for example, automobiles, medical equipment, electronic equipment, electrical equipment, information communication equipment, home appliances, audio equipment, and general industrial equipment. For example, when the composite contains permanent magnets such as Sm-Fe-N-based alloy or Nd-Fe-B-based alloy as metal powder, the composite can be used as a material for bonding magnets. When the composite contains a soft magnetic body such as a Fe-Si-Cr-based alloy as the metal powder, the composite can be used as a material for an inductor (such as an EMI filter) or a transformer (such as a seal or a magnetic core). A sheet-like molded body or cured product formed of the composite can be used as an electromagnetic wave shielding member.

<Production method of composite> The composite is obtained by mixing the metal powder and the resin composition while heating. For example, the metal powder and the resin composition can be kneaded with a kneader, a roll, a mixer, 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 entire surface of the metal particles constituting the metal powder, and coats the metal particles. By kneading, a part or all of the epoxy resin in the resin composition can be a semi-cured product.

For example, the metal powder, epoxy resin, phosphoric acid ester (dispersant), curing agent, curing accelerator, coupling agent, and wax may be kneaded in a tank at one time. The metal powder, epoxy resin, phosphate ester, curing agent, curing accelerator, coupling agent and wax may be further mixed in the tank after mixing the metal powder, at least one of the phosphoric acid ester and the coupling agent in the tank. mix up. After the metal powder, epoxy resin, phosphoric acid ester, curing agent, coupling agent, and wax are kneaded in the tank, the mixture and the curing accelerator may be further kneaded in the tank. The epoxy resin, phosphate ester, curing agent, curing accelerator, and wax can be mixed in advance to prepare resin mixed powder. The metal powder and the coupling agent can be mixed in advance to prepare the metal mixed powder. A composite can be obtained by kneading the metal mixed powder and the above-mentioned resin mixed powder.

The kneading time depends on the type of kneading machine, the volume of the kneading machine, and the production volume of the compound. The kneading time is, for example, preferably 1 minute or more, more preferably 2 minutes or more, and even more preferably 3 minutes or more. Further, the kneading time is preferably 20 minutes or less, more preferably 15 minutes or less, and even more preferably 10 minutes or less. When the kneading time is less than 1 minute, the kneading is insufficient, the moldability of the composite is impaired, and the degree of curing of the composite varies. When the kneading time exceeds 20 minutes, for example, curing of the resin composition (eg, epoxy resin and phenol resin) proceeds in the tank, and the fluidity, fillability, and moldability of the composite are likely to be impaired. When the raw materials in the tank are heated and kneaded with a kneader, the heating temperature is such that, for example, a semi-cured epoxy resin (B-stage epoxy resin) is formed and the cured epoxy resin (C-stage epoxy resin) is suppressed. Oxygen resin) can be generated at the temperature. The heating temperature may be lower than the activation temperature of the curing accelerator. The heating temperature is, for example, preferably 50°C or higher, more preferably 60°C or higher, and even more preferably 70°C or higher. The heating temperature is preferably 150°C or lower, more preferably 120°C or lower, and even more preferably 110°C or lower. When the heating temperature is within the above-mentioned range, the resin composition in the tank is softened and the surface of the metal particles constituting the metal powder is easily covered, so that the semi-cured epoxy resin is easily formed, and the epoxy resin during kneading is easily suppressed. of complete curing. [Example]

Hereinafter, the present invention will be described in further detail based on Examples and Comparative Examples. The present invention is not limited to these examples.

(Example 1) [Production of the complex] Put epoxy resin 1, epoxy resin 2, dispersant (phosphate ester), curing agent 1, curing agent 2, curing accelerator, release agent 1 (wax) and release agent 2 (wax) into a plastic container ( plastic container). The resin mixture was produced by mixing the contents of the plastic container for 10 minutes. The resin mixture corresponds to all the other components in the resin composition except for the coupling agent. As the epoxy resin 1, NC-3000 (biphenylene aralkyl type epoxy resin) manufactured by Nippon Kayaku Co., Ltd. was used. As the epoxy resin 2, TECHMORE VG3101L (trifunctional epoxy resin) manufactured by PRINTEC, INC. was used. As a dispersant, disperbyk-111 manufactured by BYK-Chemie GmbH was used. As the curing agent 1, MEHC-7500-3S (trisphenol methane type phenol resin) manufactured by Meiwa Plastic Industries, Ltd. was used. As the curing agent 2, MEHC-7851SS (biphenylene aralkyl type phenol resin) manufactured by Meiwa Plastic Industries, Ltd. was used. As a curing accelerator, U-CAT 3512T manufactured by San-Apro Ltd. was used. As the release agent 1, POWDER BASE L (zinc laurate) manufactured by NOF CORPORATION was used. As the release agent 2, LicowaxOP manufactured by Clariant Chemicals Co., Ltd. was used. Licowax OP is a montanic acid ester partially saponified by calcium hydroxide.

Iron powder 1 and iron powder 2 were uniformly mixed for 5 minutes using a pressurized biaxial kneader to prepare metal powder. Both the iron powder 1 and the iron powder 2 are amorphous. As the iron powder 1, KUAMET 9A4-II 075C03 manufactured by Epson Atmix Corporation was used. The average particle size of the iron powder 1 was 24 μm. As the iron powder 2, AW2-08 manufactured by Epson Atmix Corporation was used. The average particle size of the iron powder 2 was 5.3 μm. As a pressurized biaxial kneader, a pressurized biaxial kneader manufactured by Nihon Spindle Manufacturing Co., Ltd. was used. The capacity of the pressurized biaxial kneader was 5L.

Coupling agent 1, coupling agent 2 and additives (stress relaxation agents) were added to the metal powder in the biaxial kneader. Next, the contents of the biaxial kneader were heated to 90° C., and the contents of the biaxial kneader were mixed for 10 minutes while maintaining the temperature of the contents. Next, the above resin mixture was added to the contents of the biaxial kneader. The contents were kneaded for 15 minutes while maintaining the temperature of the contents at 120°C. After cooling the obtained kneaded material to room temperature, the kneaded material was pulverized with a hammer until the kneaded material had a predetermined particle size. As the coupling agent 1, KBM-5803 (methacryloyloxyoctyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd. was used. As the coupling agent 2, KBM-403 (3-glycidyloxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd. was used. As an additive, DBL-C32 (caprolactone-modified dimethyl silicone) manufactured by Gelest, Inc. was used.

The composite of Example 1 was produced by the above method. The mass (unit: g) of each component constituting the complex is shown in Table 1 below. The content (unit: mass %) of the metal powder in the composite is shown in Table 1 below. The content (unit: mass %) of the epoxy resin in the composite is shown in Table 1 below. The ratio (unit: part by mass) of the epoxy resin to 100 parts by mass of the metal powder is shown in Table 1 below. The ratio (unit: part by mass) of the phosphate ester (dispersant) to 100 parts by mass of the metal powder is shown in Table 1 below.

[Measurement of melt viscosity] The minimum melt viscosity of the composite at 140°C was measured as described below. As a measuring apparatus, CFT-100 (flow tester) manufactured by Shimadzu Corporation was used. As a sample for measurement, an ingot was produced from 7 g of the composite. The fluidity of the composite was evaluated under the conditions of 140° C., residual heat for 20 seconds, and a load of 100 kg. The push-in distance (unit: mm) of the plunger until the flow of the compound stopped was measured as the stroke of the flow tester. The time until the flow of the complex was stopped was measured as the flow time. Take these measurements as an indicator of liquidity. The measured melt viscosity (unit: Pa·s) of Example 1 is shown in Table 1 below.

[Measurement of circular flow] As a sample for measurement, 5 g of the composite (powder) was used. The composite is placed on the flat surface of the lower mold. A flat upper mold is pressed against the composite, and the composite is clamped by the upper mold and the lower mold. The composite between the upper mold and the lower mold was compressed for 360 seconds under a load of 8 kg, thereby forming a substantially disk-shaped molded body formed of the composite. The temperature of the composite under compression was maintained at 140°C. The maximum diameter and the minimum diameter of the disk-shaped molded body were measured. The average value of the long diameter and the short diameter corresponds to the disk flow. The disk flow (unit: mm) of Example 1 is shown in Table 1 below.

[Measurement of gel time] The gel time (gelling time) of the complex at 140°C was measured. As a measuring device (vulcanization tester) of the gel time, a curing meter (CURELASTOMETER) manufactured by JSR Corporation was used. The gel time (unit: second) of Example 1 is shown in Table 1 below.

(Examples 2 to 4 and Comparative Example 1) The mass of each component constituting the composite in each of Examples 2 to 4 and Comparative Example 1 is shown in Table 1 below. The respective composites of Examples 2 to 4 and Comparative Example 1 were produced in the same manner as in Example 1 except for the mass of each component constituting the composite. In the case of Examples 2 to 4 and Comparative Example 1, the content of the metal powder in the composite was the value shown in Table 1 below. In the case of Examples 2 to 4 and Comparative Example 1, the content of the epoxy resin in the composite was the value shown in Table 1 below. In the case of Examples 2 to 4 and Comparative Example 1, the ratio of the epoxy resin to 100 parts by mass of the metal powder is the value shown in Table 1 below. In the case of Examples 2 to 4 and Comparative Example 1, the ratio of the phosphate ester (dispersant) to 100 parts by mass of the metal powder was the value shown in Table 1 below.

In the same manner as in Example 1, the melt viscosity, disk flow, and gel time of the composites of Examples 2 to 4 and Comparative Example 1 were measured. The melt viscosity, disk flow, and gel time of each of the composites of Examples 2 to 4 and Comparative Example 1 are the values shown in Table 1 below.

【Table 1】 unit Comparative Example 1 Example 3 Example 4 Example 1 Example 2 resin composition epoxy resin 1 g 50 50 50 50 50 epoxy resin 2 g 50 50 50 50 50 Hardener 1 g 30.5 30.5 30.5 30.5 30.5 Hardener 2 g 25.0 25.0 25.0 25.0 25.0 curing accelerator g 5 5 5 5 5 Coupler 1 g 3 3 3 3 3 Coupler 2 g 2 2 2 2 2 additive g 15 15 15 15 15 Dispersant (Phosphate) g 0 3 5 1 1.5 Release agent 1 g 2 2 2 2 2 Release agent 2 g 1 1 1 1 1 mineral powder Iron powder 1 g 3798.6 3860.7 3902.1 3819.3 3829.6 Iron powder 2 g 1260.8 1281.4 1295.1 1267.7 1271.1 Complex Content of metal powder quality% 96.5 96.5 96.5 96.5 96.5 The content of epoxy resin quality% 1.91 1.88 1.86 1.90 1.89 Ratio of epoxy resin to 100 parts by mass of metal powder parts by mass 1.98 1.94 1.92 1.97 1.96 Ratio of phosphate ester to 100 parts by mass of metal powder parts by mass 0.00 0.06 0.09 0.02 0.03 fluidity melt viscosity Pa･s 1504 481 401 650 463 Disc flow mm 46 62 67 55 60 gel time Second 170 194 208 170 176 [Industrial Availability]

Since the composite of the present invention is excellent in fluidity and fillability, industrial products of various shapes such as inductors can be produced by molding the composite.

Claims (7)

A composite comprising at least a metal powder and a resin composition, The aforementioned resin composition contains at least an epoxy resin and a phosphoric acid ester, Content of the said epoxy resin in the said composite is 1.0 mass % or more and 2.0 mass % or less. The complex of claim 1, wherein The ratio of the said phosphate ester with respect to 100 mass parts of said metal powders is 0.01 mass part or more and 0.05 mass part or less. A compound as claimed in claim 1 or claim 2, wherein The melt viscosity of the composite at 140° C. is 10 Pa·s or more and 1500 Pa·s or less. The complex of any one of claim 1 to claim 3, wherein Content of the said metal powder in the said composite is 90 mass % or more and 98 mass % or less. The composite of any one of Claims 1 to 4 for use in at least one of transfer molding and compression molding. A molded body comprising the composite of any one of Claims 1 to 5. A cured product, which is a cured product of the composite according to any one of Claims 1 to 5.