Compounds, molded products and cured products

Abstract

This compound comprises 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 metal powder content of the compound is 97.0 to 97.5 mass%.

Description

[Technical Field]

[0001] One aspect of the present invention relates to a compound, a molded article, and a cured product. [Background technology]

[0002] Compounds containing metal powder and thermosetting resins are used as raw materials for various industrial products, such as inductors, depending on the physical properties of the metal powder (see Patent Documents 1 and 2 below). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Laid-Open No. 2011-211026 [Patent Document 2] Japanese Patent Application Laid-Open No. 2017-133071 Summary of the Invention [Problem to be solved by the invention]

[0004] When industrial products are manufactured from compounds, the compound is supplied and filled into a mold through a channel, and components such as coils are embedded in the compound inside the mold. These processes require the compound to have good fluidity. If the compound does not have sufficient fluidity, it will be difficult for the compound to fill the mold evenly, and voids will likely form inside the molded product formed from the compound. The fluidity of the compound improves as the metal powder content in the compound decreases.

[0005] On the other hand, in order to improve the magnetic properties of compounds used in inductors, etc., it is desirable to have a high metal powder content (filling rate) in the compound. For example, the magnetic property values ​​of the compound, such as the relative permeability and saturation magnetic flux density, increase as the metal powder content in the compound increases. However, as the metal powder content in the compound increases, the melt viscosity of the compound also increases. In particular, when the metal powder content in the compound is 97.0 mass% or more, the melt viscosity of the compound increases significantly, and the compound becomes almost non-flowable.

[0006] The present invention has been made in view of the above problems, and an object of one aspect of the present invention is to provide a compound having excellent fluidity, a molded article containing the compound, and a cured product of the compound. [Means for solving the problem]

[0007] A compound according to one aspect of the present invention is a compound comprising at least a metal powder and a resin composition, wherein the resin composition comprises at least an epoxy resin and a phosphate ester, and the content of the metal powder in the compound is 97.0 mass% or more and 97.5 mass% or less.

[0008] 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 0.10 parts by mass or less.

[0009] The melt viscosity of the compound at 140°C may be 10 Pa·s or more and 1500 Pa·s or less.

[0010] The compound according to one aspect of the present invention may be used in at least one of transfer molding and compression molding.

[0011] A molded article according to one aspect of the present invention includes the compound.

[0012] A cured product according to one aspect of the present invention is a cured product of the above-mentioned compound. [Effects of the Invention]

[0013] According to one aspect of the present invention, there are provided a compound having excellent flowability, a molded article containing the compound, and a cured product of the compound. DETAILED DESCRIPTION OF THE INVENTION

[0014] Preferred embodiments of the present invention will be described below, but the present invention is not limited to the following embodiments.

[0015] <Compound Overview> The compound according to the present embodiment includes at least a metal powder and a resin composition. That is, the compound may be a mixture of the metal powder and the resin composition. The compound may also be called a magnetic sealing material.

[0016] The metal powder is composed of a large number of metal particles. The metal powder may contain at least one selected from the group consisting of a simple metal (pure metal), an alloy, an amorphous powder, and a metal compound. The metal powder may also be referred to as a filler made of metal.

[0017] The resin composition contains at least an epoxy resin and a phosphate ester.

[0018] The epoxy resin melts at a temperature below its curing temperature, improving the fluidity of the compound. Furthermore, the epoxy resin binds the metal powder particles together through thermal curing, and also electrically insulates the metal powder particles from each other.

[0019] The phosphate ester is, for example, OP(OR 1 )(OR 2 )(OR 3 ) can be expressed as R 1 , R 2 and R 3 Each is hydrogen or any hydrocarbon group, and R 1 , R 2 and R 3At least one of the groups is a hydrocarbon group. The hydrocarbon group may be, for example, an alkyl group or an aryl group. Phosphate esters are compounds different from phosphites. Phosphite esters are, for example, P(OR 1 )(OR 2 )(OR 3 ) The resin composition may further contain a phosphite ester in addition to the phosphate ester. However, it is difficult for a compound that does not contain a phosphate ester but contains a phosphite ester to have high fluidity compared to the compound according to this embodiment. The resin composition may further contain another dispersant (for example, a coupling agent) in addition to the phosphate ester.

[0020] The phosphate ester may be a dispersant. The phosphate group of the phosphate ester is polar, so it easily adsorbs selectively to the surface of metal particles. Meanwhile, the hydrocarbon group of the phosphate ester is lipophilic, so a resin composition containing an epoxy resin is easily interposed between metal particles to which the phosphate ester is adsorbed. Therefore, the phosphate ester inhibits aggregation of metal powder, making it easier for each metal particle to disperse in the compound. In other words, the phosphate ester inhibits direct contact between metal particles, making it easier to inhibit direct friction between metal particles and the resin composition. As described above, the phosphate ester acts as a dispersant on the metal powder, improving the fluidity of the compound. For example, the inclusion of a phosphate ester in a compound reduces the melt viscosity of the compound. The fluidity of a compound containing a phosphate ester tends to be superior to that of a compound containing a dispersant other than a phosphate ester. The direct friction between metal particles may be evaluated based on the torque value measured by a gel time measuring device (vulcanization tester). The more the direct friction between metal particles is suppressed, the smaller the torque value. The gel time measuring device may be a CURELASTOMETER manufactured by JSR Corporation.

[0021] The metal powder content in the compound is 97.0% by mass or more and 97.5% by mass or less. As the metal powder content (filling rate) in the compound increases, the relative permeability and saturation magnetic flux density of the compound tend to increase. Compounds with high relative permeability and high saturation magnetic flux density are suitable, for example, as sealing materials for inductors or as raw materials for inductor cores. However, as the metal powder content in the compound increases, the melt viscosity of the compound also increases. In particular, when the metal powder content in a compound that does not contain a phosphate ester is 97.0% by mass or more, the melt viscosity of the compound increases significantly, and the compound becomes almost non-flowable. However, even when the metal powder content in the compound is 97.0% by mass or more, the compound according to this embodiment can have high fluidity (low melt viscosity) because it contains a phosphate ester along with an epoxy resin. When the metal powder content in a compound that does not contain a phosphate ester is less than 97.0% by mass, the melt viscosity of the compound is high, but the compound is still flowable. When the metal powder content in the compound is more than 97.5% by mass, the resin composition content in the compound is relatively too low, making it difficult to achieve the high fluidity inherent in the epoxy resin and phosphate ester in the resin composition, and the melt viscosity of the compound is significantly high. As a result, it becomes difficult to perform transfer molding, which requires high compound fluidity. Since the compound is likely to have high fluidity, the metal powder content in the compound may be 97.0% by mass or more and 97.3% by mass or less.

[0022] 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 0.10 parts by mass or less. When the ratio of the phosphate ester is 0.02 parts by mass or more (preferably 0.04 parts by mass or more), the compound is likely to have high fluidity (low melt viscosity) due to the phosphate ester. The phosphate ester may inhibit the curing of the epoxy resin. However, when the ratio of the phosphate ester is 0.10 parts by mass or less, the inhibition of the curing of the epoxy resin due to the phosphate ester is likely to be suppressed. In other words, when the ratio of the phosphate ester is 0.10 parts by mass or less, the gel time (curing time) of the compound is shortened. For the same reason, the ratio of the phosphate ester to 100 parts by mass of the metal powder may be 0.040 parts by mass or more and 0.060 parts by mass or less.

[0023] The melt viscosity of the compound at 140°C may be 10 Pa·s or more and 1500 Pa·s or less, 573 Pa·s or more and 1489 Pa·s or less, 573 Pa·s or more and 998 Pa·s or less, 573 Pa·s or more and 826 Pa·s or less, or 573 Pa·s or more and 633 Pa·s or less. Even if the metal powder content in the compound is 97.0 mass% or more, the compound can have such a low melt viscosity (high fluidity) by containing an epoxy resin and a phosphate ester. When the melt viscosity of the compound is within the above range, the molten compound is easily filled evenly into a mold, and defects (such as voids or burrs) in the molded body and cured product formed from the compound are easily suppressed. Therefore, compounds with such low melt viscosity are suitable for transfer molding.

[0024] The content of the epoxy resin in the compound may be 0.95% by mass or more and 1.72% by mass or less. In other words, the ratio of the epoxy resin to 100 parts by mass of the metal powder may be 0.98 parts by mass or more and 1.77 parts by mass or less. As the content of the epoxy resin in the compound increases, the fluidity of the compound tends to improve. When the content of the epoxy resin in the compound is within the above range and the compound contains a phosphate ester, the compound is likely to have high fluidity (low melt viscosity). Even when the content of the epoxy resin in the compound is within the above range, if the compound does not contain a phosphate ester, the compound is unlikely to have high fluidity. When the content of the epoxy resin in the compound is greater than the upper limit, it is difficult for the compound to achieve both magnetic properties and fluidity. Since the compound is likely to have high fluidity, the content of the epoxy resin in the compound may be 1.24% by mass or more and 1.41% by mass or less. In other words, the ratio of the epoxy resin to 100 parts by mass of the metal powder may be 1.28 parts by mass or more and 1.46 parts by mass or less.

[0025] <Compound composition details> (Resin composition) The resin composition is a component including an epoxy resin and a phosphate ester, and may be the remaining components (non-volatile components) of all components constituting the compound, excluding metal powder and organic solvents. That is, the resin composition may further contain other components in addition to the epoxy resin and the phosphate 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 a wax (mold release agent). The resin composition may further contain an additive. The additive may be, for example, a coupling agent or a flame retardant.

[0026] The resin composition functions as a binder for the metal particles that make up the metal powder, imparting mechanical strength to a molded body formed from the compound. For example, when the compound is molded under high pressure using a mold, the resin composition contained in the compound fills between the metal particles and binds the metal particles together. When the resin composition in the molded body is cured, the cured resin composition further firmly binds the metal particles together, resulting in a cured compound with excellent mechanical strength.

[0027] The resin composition may adhere to the surface of each metal particle constituting the metal powder. The resin composition may cover a portion of the surface of each metal particle, or may cover the entire surface of each metal particle. The compound may include a metal powder and an uncured resin composition. The compound may include a metal powder and a semi-cured resin composition (e.g., a B-stage resin composition). The compound may include both an uncured resin composition and a semi-cured resin composition. The compound may be a powder. The compound may be a tablet. The compound may be a paste.

[0028] The content of the resin composition in the compound is 2.5% by mass or more and 3.0% by mass or less.

[0029] [Phosphate ester] The resin composition may contain one type of phosphate ester. The resin composition may contain multiple types of phosphate esters. The phosphate ester contained in the resin composition may be at least one type of phosphate ester selected from the group consisting of phosphate monoesters, phosphate diesters, and phosphate triesters.

[0030] The phosphate ester contained in the resin composition may be at least one phosphate ester selected from the group consisting of a phosphate ester salt of a copolymer containing an acid group, compound 1 represented by the following chemical formula 1, compound 2 represented by the following chemical formula 2, compound 3 represented by the following chemical formula 3, and compound 4 represented by the following chemical formula 4. When at least one of these phosphate esters is contained in the resin composition, the compound is likely to have high fluidity. In particular, when a phosphate ester salt of a copolymer containing an acid group is contained in the resin composition, the compound is likely to have high fluidity. The phosphate ester salt of the copolymer containing an acid group may be, for example, disperbyk-111 (trade name) manufactured by BYK-Chemie GmbH. The acid value of the phosphate ester salt of the copolymer containing an acid group may be 129. The acid value of disperbyk-111 is 129. Compound 1 represented by the following chemical formula 1 may be, for example, JP-504 manufactured by Johoku Chemical Industry Co., Ltd. Compound 2 represented by the following chemical formula 2 may be, for example, JP-506H manufactured by Johoku Chemical Industry Co., Ltd. Compound 3 represented by the following chemical formula 3 may be, for example, JP-508 manufactured by Johoku Chemical Industry Co., Ltd. Compound 4 represented by the following chemical formula 4 may be, for example, JP-513 manufactured by Johoku Chemical Industry Co., Ltd. (C4H9O) n OP(OH) 3-n (1) In the above chemical formula 1, n may be 1 or 2. In the above chemical formula 1, n may be 1 or more and 3 or less. (C4H9OCH2CH2O) n OP(OH) 3-n (2) In the above chemical formula 2, n may be 1 or 2. In the above chemical formula 2, n may be 1 or more and 3 or less. (C4H9C2H5CHCH2O) n OP(OH) 3-n (3) In the above chemical formula 3, n may be 1 or 2. In the above chemical formula 3, n may be 1 or more and 3 or less. (isо‐C13 H 27 O) n OP(OH) 3-n (4) In the above chemical formula 4, n may be 1 or 2. In the above chemical formula 4, n may be 1 or more and 3 or less.

[0031] [Epoxy resin] The resin composition contains at least an epoxy resin as a thermosetting resin. The inclusion of an epoxy resin, which has relatively excellent fluidity among thermosetting resins, improves the fluidity, filling property, storage stability, and moldability of the compound. However, the compound may contain other resins in addition to the epoxy resin, as long as the effects of the present invention are not impaired. For example, the resin composition may contain at least one of a phenolic resin and a polyamide-imide resin as a thermosetting resin. When the resin composition contains both an epoxy resin and a phenolic resin, the phenolic resin may function as a curing agent for the epoxy resin. The resin composition may further contain a thermoplastic resin in addition to the thermosetting 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.

[0032] The epoxy resin may be, for example, a resin having two or more epoxy groups in one molecule. Examples of the epoxy resin include biphenyl-type epoxy resins, biphenylaralkyl-type epoxy resins, biphenylenearalkyl-type epoxy resins, stilbene-type epoxy resins, diphenylmethane-type epoxy resins, sulfur-containing epoxy resins, novolac-type epoxy resins, dicyclopentadiene-type epoxy resins, salicylaldehyde-type epoxy resins, naphthol- and phenol-copolymerized epoxy resins, epoxidized aralkyl-type phenolic resins, bisphenol-type epoxy resins, epoxy resins containing a bisphenol skeleton, glycidyl ether-type epoxy resins of alcohols, and glycidyl ether-type epoxy resins of paraxylylene and / or metaxylylene-modified phenolic resins. , glycidyl ether type epoxy resins of terpene-modified phenolic resins, cyclopentadiene type epoxy resins, glycidyl ether type epoxy resins of polycyclic aromatic ring-modified phenolic resins, glycidyl ether type epoxy resins of naphthalene ring-containing phenolic resins, glycidyl ester type epoxy resins, glycidyl or methylglycidyl type epoxy resins, alicyclic type epoxy resins, halogenated phenol novolac type epoxy resins, orthocresol novolac type epoxy resins, hydroquinone type epoxy resins, trimethylolpropane type epoxy resins, and linear aliphatic epoxy resins obtained by oxidizing an olefin bond with a peracid such as peracetic acid.

[0033] In terms of excellent fluidity, the epoxy resin may be at least one selected from the group consisting of biphenyl-type epoxy resins, orthocresol novolac-type epoxy resins, phenol novolac-type epoxy resins, bisphenol-type epoxy resins, epoxy resins having a bisphenol skeleton, salicylaldehyde novolac-type epoxy resins, and naphthol novolac-type epoxy resins.

[0034] 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 (highly crystalline epoxy resin) may be, for example, at least one selected from the group consisting of hydroquinone-type epoxy resin, bisphenol-type epoxy resin, thioether-type epoxy resin, and biphenyl-type epoxy resin. Commercially available crystalline epoxy resins include, 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-860 ... Clon 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, N 500P-2, and N500P-10 (all product 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, It may be at least one selected from the group consisting of EOCN-102S, EOCN-103S, EOCN-104S, CER-1020, EPPN-201, BREN-S, BREN-10S (all of which are trade names of Nippon Kayaku Co., Ltd.), YX-4000, YX-4000H, YL4121H, and YX-8800 (all of which are trade names of Mitsubishi Chemical Corporation).

[0035] In order to reduce the molding shrinkage of the compound, the resin composition may contain an isocyanate-modified epoxy resin as the epoxy resin. A commercially available isocyanate-modified epoxy resin may be, for example, AER-4001 manufactured by Asahi Kasei Corporation (formerly Asahi Kasei E-materials Corporation).

[0036] The resin composition may contain one type of epoxy resin from among the above. The resin composition may contain two or more types of epoxy resins from among the above.

[0037] [Hardening agent] Curing agents are classified into those that cure epoxy resins at temperatures ranging from low to room temperature, and heat-curing curing agents that cure epoxy resins when heated. Examples of curing agents that cure epoxy resins at temperatures ranging from low to room temperature include aliphatic polyamines, polyaminoamides, and polymercaptans. Examples of heat-curing curing agents include aromatic polyamines, acid anhydrides, phenol novolac resins, and dicyandiamide (DICY).

[0038] When a curing agent that cures an epoxy resin in the range from low temperature to room temperature is used, the glass transition point of the cured epoxy resin tends to be low and the cured epoxy resin tends to be soft. As a result, a molded body formed from the compound also tends to be soft. On the other hand, from the viewpoint of improving the heat resistance of the molded body, the curing agent may preferably be a heat-curing type curing agent, more preferably a phenolic resin, and even more preferably a phenolic novolac resin. In particular, by using a phenolic novolac resin as a curing agent, it is easy to obtain a cured epoxy resin with a high glass transition point. As a result, the heat resistance and mechanical strength of the molded body are easily improved.

[0039] The phenolic resin may be at least one selected from the group consisting of aralkyl phenolic resins, dicyclopentadiene phenolic resins, salicylaldehyde phenolic resins, novolac phenolic resins, copolymerized phenolic resins of benzaldehyde phenols and aralkyl phenols, paraxylylene and / or metaxylylene-modified phenolic resins, melamine-modified phenolic resins, terpene-modified phenolic resins, dicyclopentadiene naphthol resins, cyclopentadiene-modified phenolic resins, polycyclic aromatic ring-modified phenolic resins, biphenyl phenolic resins, and triphenylmethane phenolic resins. The phenolic resin may also be a copolymer composed of two or more of the above.

[0040] The phenol novolac resin may be, for example, a resin obtained by condensing or co-condensing phenols and / or naphthols with aldehydes under an acidic catalyst. The phenols constituting the phenol novolac resin may be, for example, at least one selected from the group consisting of phenol, cresol, xylenol, resorcinol, catechol, bisphenol A, bisphenol F, phenylphenol, and aminophenol. The naphthols constituting the phenol novolac 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 novolac resin may be, for example, at least one selected from the group consisting of formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde, and salicylaldehyde.

[0041] 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.

[0042] The resin composition may contain one type of phenolic resin from among the above. The resin composition may contain multiple types of phenolic resins from among the above. The resin composition may contain one type of curing agent from among the above. The resin composition may contain multiple types of curing agents from among the above.

[0043] The ratio of active groups (phenolic OH groups) in the curing agent that react with epoxy groups in the epoxy resin may be preferably 0.5 to 1.5 equivalents, more preferably 0.6 to 1.4 equivalents, and even more preferably 0.8 to 1.2 equivalents per equivalent of epoxy groups in the epoxy resin. If the ratio of active groups in the curing agent is less than 0.5 equivalents, it is difficult to obtain a sufficient elastic modulus of the resulting cured product. On the other hand, if the ratio of active groups in the curing agent is more than 1.5 equivalents, the mechanical strength of a molded article formed from the compound after curing tends to decrease.

[0044] [Curing accelerator] The curing accelerator is not limited as long as it is a composition that reacts with the epoxy resin to accelerate the curing of the epoxy resin. The curing accelerator may be, for example, an alkyl group-substituted imidazole or an imidazole such as benzimidazole. The resin composition may contain one type of curing accelerator. The resin composition may contain multiple types of curing accelerators. When the resin composition contains a curing accelerator, the moldability and releasability of the compound are likely to be improved. Furthermore, when the resin composition contains a curing accelerator, the mechanical strength of a molded product (e.g., electronic component) produced using the compound is improved, and the storage stability of the compound under high temperature and / or high humidity environments is improved. As a commercially available imidazole curing accelerator, for example, at least one selected from the group consisting of 2MZ-H, C11Z, C17Z, 1,2DMZ, 2E4MZ, 2PZ-PW, 2P4MZ, 1B2MZ, 1B2PZ, 2MZ-CN, C11Z-CN, 2E4MZ-CN, 2PZ-CN, C11Z-CNS, 2P4MHZ, TPZ, and SFZ (all of which are trade names manufactured by Shikoku Chemicals Corporation) may be used.

[0045] The amount of the curing accelerator to be added is not particularly limited as long as it is an amount that can achieve a curing acceleration effect. However, from the viewpoint of improving the curability and fluidity of the resin composition when absorbing moisture, the amount of the curing accelerator to be added may be preferably 0.1 to 30 parts by mass, more preferably 1 to 15 parts by mass, per 100 parts by mass of the epoxy resin. The content of the curing accelerator is preferably 0.001 to 5 parts by mass, per 100 parts by mass of the total mass of the epoxy resin and the curing agent (e.g., phenolic resin). If the amount of the curing accelerator to be added is less than 0.1 part by mass, it is difficult to achieve a sufficient curing acceleration effect. If the amount of the curing accelerator to be added exceeds 30 parts by mass, the storage stability of the compound is likely to decrease.

[0046] [Coupling agent] The coupling agent improves the adhesion between the resin composition and the metal particles constituting the metal powder, thereby improving the flexibility and mechanical strength of the 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. The silane coupling agent may be, for example, at least one selected from the group consisting of epoxy silane, mercapto silane, amino silane, alkyl silane, ureido silane, acid anhydride silane, and vinyl silane. Aminophenyl-based silane coupling agents are particularly preferred. The resin composition may contain one or more of the above coupling agents. Commercially available coupling agents include, for example, vinyltrimethoxysilane (KBM-1003), vinyltriethoxysilane (KBE-1003), 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane (KBM-303), 3-glycidoxypropylmethyldimethoxysilane (KBM-402), 3-glycidoxypropyltrimethoxysilane (KBM-403), p-styryltrimethoxysilane (KBM-1403), 3-methacryloxypropylmethyldimethoxysilane (KBM-502), 3-methacryloxypropyltrimethoxysilane (KBM-503), and the like. ), 3-methacryloxypropylmethyldiethoxysilane (KBE-502), 3-methacryloxypropyltriethoxysilane (KBE-503), 3-acryloxypropyltrimethoxysilane (KBM-5103), N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane (KBM-602), N-2-(aminoethyl)-3-aminopropyltrimethoxysilane (KBM-603), 3-aminopropyltrimethoxysilane (KBM-903), 3-aminopropyltriethoxysilane (KBE-903), 3-triethoxysilyl-N-(1,3-Dimethyl-butylidene)propylamine (KBE-9103), N-phenyl-3-aminopropyltrimethoxysilane (KBM-573), N-vinylbenzyl-2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride (KBM-575), tris-(trimethoxysilylpropyl)isocyanurate (KBM-9659), 3-ureidopropyltrialkoxysilane (KBE-585), 3-mercaptopropylmethyldimethoxysilane (KBM-802), 3-mercaptopropyltrimethoxysilane (KBM-803), 3-isocyanatopropyltriethoxysilane (KBM-9007), octenyltrimethoxysilane (KBM-1083), glycidoxyoctyltrimethoxysilane (KBM-4803), methacryloxyoctyltrimethoxysilane (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), hexyltrimethoxysilane (KBM-3063), hexyltriethoxysilane (KBE-3063), octyltriethoxysilane (KBE-3083), decyltrimethoxysilane (KBM-3103C), 1,The coupling agent may be at least one selected from the group consisting of 6-(trimethoxysilyl)hexane (KBM-3066), trifluoropropyltrimethoxysilane (KBM-7103), hexamethyldisilazane (SZ-31), and hydrolyzable group-containing siloxane (KPN-3504) (all of which are product names manufactured by Shin-Etsu Chemical Co., Ltd.). The coupling agent may be a silicone alkoxy oligomer (a silicone oligomer having an alkoxy group). The silicone alkoxy oligomer may have at least one alkoxy group selected from the group consisting of a methoxy group and an ethoxy group. The silicone alkoxy oligomer may have at least one organic substituent selected from the group consisting of an epoxy group, a methyl group, a mercapto group, an acryloyl group, a methacryloyl group, a vinyl group, and a phenyl group. The silicone alkoxy oligomer may be, for example, at least one selected from the group consisting of KR-517, X-41-1059A, X-24-9590, KR-516, X-41-1805, X-41-1818, X-41-1810, 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-40-9227, KR-510, KR-9218, and KR-213 (all of which are trade names manufactured by Shin-Etsu Chemical Co., Ltd.).

[0047] [wax] The wax increases the fluidity of the compound during molding (e.g., transfer molding) of the compound and also functions as a mold release agent. The wax may be at least one of a fatty acid such as a higher fatty acid, a fatty acid ester, and a fatty acid salt.

[0048] Examples of waxes include fatty acids such as montanic acid, stearic acid, 12-hydroxystearic acid, and lauric acid, and esters thereof; fatty acid salts such as zinc stearate, calcium stearate, barium stearate, aluminum stearate, magnesium stearate, zinc laurate, calcium laurate, zinc linoleate, calcium ricinoleate, and zinc 2-ethylhexoate; and fatty acid salts such as stearic acid amide, oleic acid amide, erucic acid amide, behenic acid amide, palmitic acid amide, lauric acid amide, hydroxystearic acid amide, methylene bisstearic acid amide, ethylene bisstearic acid amide, ethylene bislauric acid amide, distearyl adipate amide, ethylene bisoleic acid amide, dioleyl adipate amide, and N-stearyl stearin. fatty acid esters such as butyl stearate; alcohols such as ethylene glycol and stearyl alcohol; polyethers such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol and modified products thereof; polysiloxanes such as silicone oil and silicone grease; 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 wax and microcrystalline wax.

[0049] [Other components in the resin composition] The compound may contain a flame retardant to improve the environmental safety, recyclability, moldability, and low cost of the compound. The flame retardant may be, for example, at least one selected from the group consisting of 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 engineering plastics. The resin composition may contain one or more of the above flame retardants.

[0050] (metal powder) The metal powder may contain, for example, at least one selected from the group consisting of an elemental metal (pure metal) and an alloy. The metal powder may be, for example, at least one selected from the group consisting of an elemental metal (pure metal), an alloy, an amorphous powder, and a metal compound. The alloy may 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 alloy, Fe-Ni-Cr alloy, etc.). The metal powder may contain one metal element or multiple metal elements. The metal element contained in the metal powder may be, for example, a base metal element, a noble metal element, a transition metal element, or a rare earth element. The compound may contain one metal powder or multiple metal powders.

[0051] The metal element contained in the metal powder may be, for example, at least one selected from the group consisting of 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), praseodymium (Pr), neodymium (Nd), samarium (Sm), and dysprosium (Dy). The metal powder may also contain elements other than metal elements. For example, the metal powder may contain oxygen (O), 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. The metal powder may be, for example, a magnetic powder consisting of at least one selected from the group consisting of Fe-Si alloys, Fe-Si-Al alloys (Sendust), Fe-Ni alloys (Permalloy), Fe-Cu-Ni alloys (Permalloy), Fe-Co alloys (Permendur), Fe-Cr-Si alloys (electromagnetic stainless steel), Nd-Fe-B alloys (rare earth magnets), Sm-Fe-N alloys (rare earth magnets), and Al-Ni-Co alloys (Alnico magnets). The metal powder may also be a copper alloy such as a Cu-Sn alloy, a Cu-Sn-P alloy, a Cu-Ni alloy, or a Cu-Be alloy. The metal powder may consist of only one type of element or composition. The metal powder may also contain multiple types of elements or compositions.

[0052] The metal powder may be Fe elemental (pure iron). The metal powder may be an alloy containing iron (Fe-based alloy). The Fe-based alloy may be, for example, an Fe-Si-Cr-based alloy, an Nd-Fe-B-based alloy, or an Sm-Fe-N-based alloy. The metal powder may be at least one of amorphous iron powder and carbonyl iron powder. When the metal powder contains at least one of Fe elemental and an Fe-based alloy, it is easy to produce a molded body from the compound that has a high space factor and excellent magnetic properties. The metal powder may be an Fe amorphous alloy. As a commercially available product of Fe amorphous alloy powder, for example, at least one selected from the group consisting of AW2-08, KUAMET-6B2 (all of which are trade names of Epson Atmix Corporation), DAP MS3, DAP MS7, DAP MSA10, DAP PB, DAP PC, DAP MKV49, DAP 410L, DAP 430L, DAP HYB series (all of which are trade names of Daido Steel Co., Ltd.), MH45D, MH28D, MH25D, and MH20D (all of which are trade names of Kobe Steel, Ltd.) may be used.

[0053] The average particle size 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 size may be measured, for example, using a particle size distribution analyzer. The shape of the individual metal particles constituting the metal powder is not limited, but may be, for example, spherical, flat, prismatic, or acicular. The compound may contain multiple types of metal powders with different average particle sizes.

[0054] <Uses of the compound> The compound may be used for at least one of transfer molding and compression molding. Transfer molding is a type of injection molding method for thermosetting resins. Transfer molding may also be referred to as pressure molding. Transfer molding may include the steps of heating and fluidizing the compound in a heating chamber, feeding (pressing) the fluidized compound from the heating chamber into a mold through a casting runner, and heating and curing the compound in the mold. Transfer molding may include the steps of heating and fluidizing the compound in a heating chamber, feeding the fluidized compound powder from the heating chamber into a plunger, feeding (pressing) the compound from the plunger into a mold through the runner, and heating and curing the compound in the mold. The pressure applied to the compound during transfer molding may be, for example, 3 MPa or more and 100 MPa or less. The compound according to this embodiment exhibits excellent fluidity and filling properties when heated, so it flows easily through narrow runners and is easily filled evenly into the space (cavity) in the mold. Therefore, by processing the compound by transfer molding, it is possible to produce molded products and cured products with few defects such as voids or burrs. The compound may be molded by compression molding.

[0055] Depending on the composition or combination of metal powders contained in the compound, the properties (e.g., electromagnetic properties or magnetic properties) of the molded body and cured body formed from the compound can be freely controlled. Therefore, the molded body and cured body can be used for various industrial products or their raw materials. The molded body formed from the compound may contain at least one of an uncured resin composition and a B-stage resin composition (semi-cured resin composition). The molded body may consist only of the compound. The cured product of the compound or molded body may contain a C-stage resin composition (cured resin composition).

[0056] Industrial products manufactured using the compound may include, for example, automobiles, medical devices, electronic devices, electrical devices, information and communication devices, home appliances, audio equipment, and general industrial equipment. For example, when the compound contains a permanent magnet such as an Sm-Fe-N alloy or an Nd-Fe-B alloy as the metal powder, the compound may be used as a material for a bonded magnet. When the compound contains a soft magnetic material such as an Fe-Si-Cr alloy as the metal powder, the compound may be used as a material for an inductor (e.g., an EMI filter) or a transformer (e.g., a sealant or a magnetic core). A sheet-shaped molded body or a cured product formed from the compound may be used as an electromagnetic wave shield.

[0057] <Compound manufacturing method> A compound can be 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, roll, agitator, or the like while heating. By heating and mixing the metal powder and the resin composition, the resin composition adheres to part or all of the surface of each metal particle constituting the metal powder, coating each metal particle. By kneading, part or all of the epoxy resin in the resin composition can become semi-cured.

[0058] For example, metal powder, epoxy resin, phosphate ester (dispersant), curing agent, curing accelerator, coupling agent, and wax may be kneaded together in a tank. After mixing metal powder and at least one of phosphate ester and coupling agent in a tank, metal powder, epoxy resin, phosphate ester, curing agent, curing accelerator, coupling agent, and wax may be further kneaded in the tank. After kneading metal powder, epoxy resin, phosphate ester, curing agent, coupling agent, and wax in a tank, this mixture and curing accelerator may be further kneaded in the tank. The epoxy resin, phosphate ester, curing agent, curing accelerator, and wax may be mixed in advance to prepare a resin mixed powder. The metal mixed powder may be prepared in advance by mixing the metal powder and coupling agent. The metal mixed powder and the above-mentioned resin mixed powder may be kneaded to obtain a compound.

[0059] The kneading time depends on the type of kneading machine, the capacity of the kneading machine, and the amount of compound produced. 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. The kneading time is preferably 20 minutes or less, more preferably 15 minutes or less, and even more preferably 10 minutes or less. If the kneading time is less than 1 minute, the kneading is insufficient, the compound's moldability is impaired, and the degree of cure of the compound varies. If the kneading time exceeds 20 minutes, for example, the resin composition (e.g., epoxy resin and phenolic resin) is cured in the tank, which is likely to impair the fluidity, filling ability, and moldability of the compound. When the raw materials in the tank are kneaded using a kneader while being heated, the heating temperature may be, for example, a temperature at which a semi-cured epoxy resin (B-stage epoxy resin) is produced and the production of a cured epoxy resin (C-stage epoxy resin) is suppressed. The heating temperature may be lower than the activation temperature of the curing accelerator. The heating temperature is, for example, preferably 50° C. or higher, more preferably 60° C. or higher, and even more preferably 70° C. or higher. The heating temperature is preferably 150° C. or lower, more preferably 120° C. or lower, and even more preferably 110° C. or lower. When the heating temperature is within the above range, the resin composition in the tank softens and tends to coat the surfaces of the metal particles that make up the metal powder, making it easier to produce a semi-cured epoxy resin and to inhibit complete curing of the epoxy resin during kneading. [Example]

[0060] The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to these examples in any way.

[0061] Example 1 [Making the compound] 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) were placed in a plastic container. The contents of the plastic container were mixed for 10 minutes to prepare a resin mixture. The resin mixture corresponds to all components of 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 Co., Ltd. was used. The dispersant used was disperbyk-111 manufactured by BYK-Chemie GmbH. As the curing agent 1, MEHC-7500-3S (triphenolmethane type phenolic resin) manufactured by Meiwa Kasei Co., Ltd. was used. As the curing agent 2, MEHC-7851SS (biphenylene aralkyl type phenol resin) manufactured by Meiwa Kasei Co., Ltd. was used. As the curing accelerator, 2E4MZ (2-ethyl-4-methylimidazole) manufactured by Shikoku Chemicals Corporation was used. Licowax OP manufactured by Clariant Chemicals Co., Ltd. was used as the release agent 1. Licowax OP is a montanic acid ester that is partially saponified with calcium hydroxide. As the release agent 2, zinc stearate manufactured by NOF Corporation was used.

[0062] Iron powder 1 and iron powder 2 were mixed uniformly for 5 minutes in a pressure twin-screw kneader to prepare a metal powder. Both iron powder 1 and iron powder 2 were amorphous. KUAMET 9A4-II 075C03 manufactured by Epson Atmix Corporation was used as iron powder 1. The average particle size of iron powder 1 was 24 μm. AW2-08 manufactured by Epson Atmix Corporation was used as iron powder 2. The average particle size of iron powder 2 was 5.3 μm. The pressure twin-screw kneader used was a pressure twin-screw kneader manufactured by Nihon Spindle Mfg. Co., Ltd. The capacity of the pressure twin-screw kneader was 5 L.

[0063] Coupling agent 1, coupling agent 2, and an additive (stress relaxation agent) were added to the metal powder in the twin-screw kneader. The contents of the twin-screw kneader were then heated to 90°C, and the contents of the twin-screw kneader were mixed for 10 minutes while maintaining the temperature of the contents. The resin mixture was then added to the contents of the twin-screw kneader. The contents were kneaded for 15 minutes while maintaining the temperature of the contents at 120°C. The resulting kneaded mixture was then cooled to room temperature, and then pulverized with a hammer until it reached the desired particle size. As coupling agent 1, KBM-5803 (methacryloxyoctyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd. was used. As the coupling agent 2, KBM-403 (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd. was used. As the additive, DBL-C32 (caprolactone-modified dimethyl silicone) manufactured by Gelest Co., Ltd. was used.

[0064] The compound of Example 1 was prepared by the above method. The mass (unit: g) of each component constituting the compound is shown in Table 1 below. The content (unit: mass %) of metal powder in the compound is shown in Table 1 below. The content (unit: mass %) of the epoxy resin in the compound is shown in Table 1 below. The ratio (unit: parts by mass) of epoxy resin to 100 parts by mass of metal powder is shown in Table 1 below. The ratio (unit: parts by mass) of phosphate ester (dispersant) to 100 parts by mass of metal powder is shown in Table 1 below.

[0065] [Melt viscosity measurement] The minimum melt viscosity of the compound at 140°C was measured as follows. The measurement device used was a CFT-100 (flow tester) manufactured by Shimadzu Corporation. Tablets were prepared from 7 g of the compound as measurement samples. The fluidity of the compound was evaluated under conditions of 140°C, 20 seconds of preheating, and a load of 100 kg. The plunger depression distance (unit: mm) until the compound stopped flowing was measured as the flow tester stroke. The time until the compound stopped flowing was measured as the flow time. These measured values ​​were used as indicators of fluidity. The measured melt viscosities (unit: Pa s) of Example 1 are shown in Table 1 below.

[0066] [Disk flow measurement] 5 g of compound (powder) was used as the measurement sample. The compound was placed on the flat surface of the lower mold. A flat upper mold was pressed against the compound, and the compound was sandwiched between the upper and lower molds. The compound was compressed between the upper and lower molds with a load of 8 kg for 360 seconds to form a roughly disk-shaped molded body made of the compound. The temperature of the compound during compression was maintained at 140°C. The maximum and minimum diameters of the disk-shaped molded body were measured. The average value of the major and minor diameters corresponds to the disk flow. The disk flow (unit: mm) of Example 1 is shown in Table 1 below.

[0067] (Examples 2 to 5 and Comparative Examples 1 to 3) The mass of each component constituting the compounds of Examples 2 to 5 and Comparative Examples 1 to 3 is shown in the following Table 1. The compounds of Examples 2 to 5 and Comparative Examples 1 to 3 were prepared in the same manner as Example 1, except for the mass of each component constituting the compound. In the cases of Examples 2 to 5 and Comparative Examples 1 to 3, the content of metal powder in the compound was the value shown in Table 1 below. In the cases of Examples 2 to 5 and Comparative Examples 1 to 3, the content of the epoxy resin in the compound was the value shown in Table 1 below. In the cases of Examples 2 to 5 and Comparative Examples 1 to 3, the ratio of epoxy resin to 100 parts by mass of metal powder was the value shown in Table 1 below. In the cases of Examples 2 to 5 and Comparative Examples 1 to 3, the ratio of the phosphate ester (dispersant) to 100 parts by mass of the metal powder was the value shown in Table 1 below.

[0068] The melt viscosity and disk flow of each of the compounds of Examples 2 to 5 and Comparative Examples 1 to 3 were measured using the same method as in Example 1. The melt viscosity and disk flow of each of the compounds of Examples 2 to 5 and Comparative Examples 1 to 3 were the values ​​shown in Table 1 below. However, in the case of Comparative Examples 2 and 3, the compounds hardly flowed, making it difficult to measure the melt viscosity. In other words, in the case of Comparative Examples 2 and 3, the melt viscosity was so high that it was difficult to measure.

[0069] [Table 1] [Industrial Applicability]

[0070] The compound according to the present invention has excellent fluidity and filling properties, and therefore can be molded to produce industrial products of various shapes, such as inductors.

Claims

1. A compound containing at least a metal powder and a resin composition, the metal powder is a soft magnetic material and is at least one of pure iron and an Fe-based alloy containing iron, the resin composition contains at least an epoxy resin and a phosphate ester, The content of the metal powder in the compound is 97.0% by mass or more and 97.5% by mass or less, a ratio of the phosphate ester to 100 parts by mass of the metal powder is 0.02 parts by mass or more and 0.10 parts by mass or less; Compound.

2. The content of the epoxy resin in the compound is 0.95% by mass or more and 1.72% by mass or less. The compound of claim 1.

3. The melt viscosity of the compound at 140°C is 10 Pa s or more and 1500 Pa s or less.

3. The compound according to claim 1 or 2.

4. a ratio of the epoxy resin to 100 parts by mass of the metal powder is 0.98 parts by mass or more and 1.77 parts by mass or less; The compound according to any one of claims 1 to 3.

5. Used in inductors, transformers, or electromagnetic wave shielding, A compound according to any one of claims 1 to 4.

6. It is a sealing material for inductors and a raw material for inductor magnetic cores. A compound according to any one of claims 1 to 4.

7. the phosphate ester is at least one phosphate ester selected from the group consisting of a phosphate ester salt of a copolymer containing an acid group, compound 1 represented by the following chemical formula 1, compound 2 represented by the following chemical formula 2, compound 3 represented by the following chemical formula 3, and compound 4 represented by the following chemical formula 4, (C ４ H ９ O) ｎ OP(OH) ３－ｎ (1) (C) ４ H ９ OCH ２ CH ２ O) ｎ OP (OH) ３－ｎ (2) (3 ４ 8 ９ 3 ２ 8 ５ 3832 ２ 9) ｎ 90(98) ３－ｎ (3) (ISO-C) １３ H ２７ O) ｎ OP (OH) ３－ｎ (4) In the above Chemical Formula 1, n is 1 or more and 3 or less, In the above Chemical Formula 2, n is 1 or more and 3 or less, In the above Chemical Formula 3, n is 1 or more and 3 or less, In the chemical formula 4, n is 1 or more and 3 or less. A compound according to any one of claims 1 to 6.

8. The epoxy resin is a biphenyl aralkyl epoxy resin. A compound according to any one of claims 1 to 7.

9. The resin composition further comprises a curing agent, the curing agent is at least one selected from the group consisting of triphenolmethane type phenolic resins, aralkyl type phenolic resins, and biphenyl type phenolic resins; A compound according to any one of claims 1 to 8.

10. The resin composition further contains a curing accelerator. A compound according to any one of claims 1 to 9.

11. The resin composition further contains a wax, The wax is at least one selected from the group consisting of Montan acid ester partially saponified with calcium hydroxide and zinc stearate. A compound according to any one of claims 1 to 10.

12. The resin composition further comprises a coupling agent, The coupling agent is at least one selected from the group consisting of methacryloxyoctyltrimethoxysilane and 3-glycidoxypropyltrimethoxysilane. A compound according to any one of claims 1 to 11.

13. The resin composition further contains caprolactone-modified dimethyl silicone. A compound according to any one of claims 1 to 12.

14. Comprising a compound according to any one of claims 1 to 13, Molded body.

15. A cured product of the compound according to any one of claims 1 to 13.

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