CN111406085B - Composite powder - Google Patents
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- CN111406085B CN111406085B CN201780097276.8A CN201780097276A CN111406085B CN 111406085 B CN111406085 B CN 111406085B CN 201780097276 A CN201780097276 A CN 201780097276A CN 111406085 B CN111406085 B CN 111406085B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
Abstract
The invention provides a composite powder having excellent fluidity, storage stability and moldability. The composite powder contains a metal element-containing powder, an epoxy resin, and a curing agent, and the content of a solid residue remaining after the composite powder is dissolved in a ketone solvent is 98.5 mass% or more and 99.5 mass% or less.
Description
Technical Field
The invention relates to a composite powder.
Background
Composite powders comprising a metal powder and a thermosetting resin are used as raw materials for various industrial products such as inductors, electromagnetic wave shielding materials, and bonded magnets, depending on the physical properties of the metal powder (see patent documents 1 and 2 below).
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open publication No. 2009-260116
Patent document 2: japanese unexamined patent publication No. 2014-013803
Disclosure of Invention
Problems to be solved by the invention
In the case of manufacturing an industrial product from the composite powder, the composite powder is supplied and filled into a mold, or a member such as a coil is embedded in the composite powder in the mold. In these processes, the composite powder is required to have fluidity. Here, the fluidity means a property that at least a part of the thermosetting resin in the heated composite powder is softened or liquefied, and the entire composite powder becomes easy to flow. The higher the curing temperature of the thermosetting resin contained in the composite powder is, the more easily the curing of the thermosetting resin is suppressed, and the more easily the thermosetting resin is softened or liquefied by heating, the more easily the fluidity of the composite powder is improved. However, a molded body formed of the composite powder excellent in fluidity is soft. That is, the higher the fluidity of the composite powder is, the less the hardness (moldability) of the uncured molded article formed from the composite powder is. In the production process of an industrial product using the composite powder, the molded body may have to be processed or transported before the thermosetting resin in the molded body is completely cured, but the flexible molded body is easily broken along with the processing or transportation. For the above reasons, it is difficult to achieve both flowability and moldability in conventional composite powders. In addition, the fluidity of conventional composite powders tends to decrease when the composite powders are stored for a long time. Therefore, the composite powder is also required to have a property (storage stability) that fluidity is not easily deteriorated during storage.
The purpose of the present invention is to provide a composite powder having excellent flowability, storage stability and moldability.
Means for solving the problems
The composite powder according to one aspect of the present invention includes a metal element-containing powder, an epoxy resin, and a curing agent, wherein a content of a solid residue remaining after the composite powder is dissolved in a ketone solvent is 98.5 mass% or more and 99.5 mass% or less.
The solid-component residue may contain a semi-solidified product of the epoxy resin and a metal element-containing powder.
The composite powder of one aspect of the present invention may contain a curing accelerator.
In one aspect of the present invention, the curing accelerator may be at least one of a borate and a borane compound.
The composite powder of another aspect of the present invention includes a metallic element-containing powder, an epoxy resin, a curing agent, and a curing accelerator, wherein the curing accelerator is at least one of a borate and a borane compound.
The borate may be represented by the following general formula (1).
X + B - (R) 4 (1)
In the general formula (1), X is at least one selected from alkyl phosphonium salts, aryl phosphonium salts, imidazole salts, salts of imidazole derivatives, tertiary amine salts and quaternary ammonium salts, B is boron, and R is at least one selected from alkyl groups, aryl groups and fluorine groups.
The borane compound can be represented by the following general formula (2).
Y·B(R) 3 (2)
In the general formula (2), Y is at least one selected from alkyl phosphine, aryl phosphine, imidazole derivatives and tertiary amine, B is boron, and R is at least one selected from alkyl, aryl and fluoro.
The composite powder may comprise a wax.
The metal-containing powder may be at least one selected from the group consisting of Sm-Co alloy powder, fe-Co alloy powder, sm-Fe-N alloy powder, ferrite powder, amorphous iron powder and carbonyl iron powder.
The content of the metal element-containing powder may be 92.0 mass% or more and 99.0 mass% or less.
The epoxy resin may be at least one selected from the group consisting of a biphenyl type epoxy resin, an o-cresol novolac type epoxy resin, a phenol novolac type epoxy resin, a salicylaldehyde novolac type epoxy resin, and a naphthol novolac type epoxy resin.
The composite powder may be used for a magnetic core.
The composite powder may be used for transfer molding.
Effects of the invention
According to the present invention, a composite powder excellent in flowability, storage stability and moldability can be provided.
Detailed Description
Preferred embodiments of the present invention will be described below. However, the present invention is not limited to the following embodiments.
The composite powder of the present embodiment includes a metal element-containing powder, an epoxy resin, and a curing agent. The content of the solid residue remaining after the composite powder is dissolved in the ketone solvent is 98.5 mass% to 99.5 mass% based on the total mass of the composite powder. In other words, the content of the solid content residue remaining undissolved in the ketone solvent after the addition of the composite powder to the ketone solvent is 98.5 mass% or more and 99.5 mass% or less with respect to the total mass of the composite powder. By setting the content of the solid content residue to 98.5 mass% or more and 99.5 mass% or less, the flowability, storage stability and moldability of the composite powder are improved. When the content of the solid content residue is less than 98.5% by mass, an uncured molded body formed from the composite powder is too soft. That is, the composite powder having an excessively small content of the solid content residue has inferior moldability to that of the present embodiment. Further, the fluidity of the composite powder having a solid content residue content of less than 98.5 mass% tends to decrease with storage. On the other hand, the composite powder having a solid content residue content of more than 99.5 mass% hardly contains a component (for example, an uncured epoxy resin) softened or liquefied by heating, and therefore has poor fluidity as compared with the present embodiment. That is, the larger the content of the solid content residue, the more likely the composite powder is to agglomerate, and the lower the flowability of the composite powder is. The content of the solid content residue may be 99.0 mass% or more and 99.5 mass% or less from the viewpoint of improving the fluidity, storage stability and moldability of the composite powder.
The solid-content residue may contain a semi-cured product of the epoxy resin (B-stage epoxy resin) and a metal element-containing powder. The main components of the solid content residue may be a semi-cured product of the epoxy resin and a metal element-containing powder. The solid content residue may further contain at least one selected from the group consisting of a curing agent (a curing agent that reacts with the epoxy resin), a curing accelerator, a coupling agent, and a flame retardant, in addition to the semi-cured product of the epoxy resin and the metal element-containing powder. Among the components contained in the composite powder, the component which is easily dissolved in the ketone solvent (the component which is hardly contained in the solid residue) may be, for example, an uncured epoxy resin. Among the components contained in the composite powder, those which are likely to be dissolved in the ketone solvent may be, for example, at least one selected from a curing agent (unreacted curing agent), a curing accelerator, a coupling agent and a flame retardant, and an uncured epoxy resin.
The ketone solvent for dissolving the composite powder is not particularly limited as long as it is a ketone dissolved in the uncured epoxy resin, and may be at least one selected from the group consisting of acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclohexanone, and diacetone alcohol.
The composite powder may include a curing accelerator. The composite powder may comprise one or more cure accelerators. The curing accelerator is not limited as long as it is a composition that, for example, reacts with an epoxy resin to accelerate the curing of the epoxy resin. By including the curing accelerator in the composite powder, moldability and releasability of the composite powder are easily improved. Further, when the composite powder contains a curing accelerator, the mechanical strength of a molded article (for example, an electronic component such as an inductor) produced using the composite powder is improved, or the storage stability of the composite powder in a high-temperature and high-humidity environment is improved.
The curing accelerator may be, for example, at least one of a borate and a borane compound. That is, the composite powder according to another aspect of the present embodiment includes a metal element-containing powder, an epoxy resin, a curing agent, and a curing accelerator, and the curing accelerator may be at least one of a borate and a borane compound. A composite powder containing at least one of a borate and a borane compound is superior in flowability, storage stability, and moldability to a composite powder containing other curing accelerators (e.g., imidazoles).
By heating the composite powder at a temperature lower than the activation temperature of the curing accelerator, the epoxy resin in the composite powder is inhibited from curing, and the epoxy resin is softened or liquefied to improve the fluidity of the entire composite powder. In other words, the higher the activation temperature of the curing accelerator, the more easily the curing of the epoxy resin accompanied by the fluidization of the composite powder is suppressed. At the same time, the molded body formed of the composite powder having high flowability is softer. That is, the higher the activation temperature of the curing accelerator is, the higher the fluidity of the composite powder is, and the hardness (moldability) of the uncured molded article formed from the composite powder tends to be insufficient. Therefore, in the case of the conventional composite powder, it is difficult to use a curing accelerator having a high activation temperature such as a borate or a borane compound. On the other hand, since the composite powder of the present embodiment contains the solid residue (the semi-cured product of the epoxy resin or the like) in the above content, the fluidity of the composite powder is appropriately suppressed, and the hardness (moldability) of the uncured molded body formed of the composite powder can be improved. In other words, even when the composite powder contains a curing accelerator having a high activation temperature such as a borate or a borane compound, the hardness (moldability) of the uncured molded article can be improved by making at least a part (preferably most) of the epoxy resin in the composite powder a semi-cured material. For the above reasons, according to the present embodiment, a curing accelerator having a high activation temperature, which has been conventionally difficult to add to composite powder, can be used. In other words, according to the present embodiment, since the option of the curing accelerator is hardly limited by its activation temperature, the degree of freedom of selection of the curing accelerator increases, and the degree of freedom of design of the composite powder increases.
The borate used as the curing accelerator may be represented by the following general formula (1).
X + B - (R) 4 (1)
In the general formula (1), X is at least one selected from alkyl phosphonium salt, aryl phosphonium salt, imidazole salt, salt of imidazole derivative, tertiary amine salt and quaternary ammonium salt, B is boron, and R is at least one selected from alkyl, aryl and fluorine group.
The borate represented by the general formula (1) may be at least one selected from tetrabutylphosphonium tetraphenylborate, tetraphenylphosphonium-tetrakis (4-methylphenyl) borate, tetraphenylphosphonium-tetraphenylborate, tetraphenylphosphonium-tetra-p-tolylborate, and tri-tert-butylphosphine-tetraphenylborate, for example.
The borane compound used as the curing accelerator may be represented by the following general formula (2).
Y·B(R) 3 (2)
In the general formula (2), Y is at least one selected from alkyl phosphine, aryl phosphine, imidazole derivative and tertiary amine, B is boron, and R is at least one selected from alkyl, aryl and fluoro.
The borane compound represented by the general formula (2) may be at least one selected from the group consisting of triphenylphosphine triphenylborane, 2-methylimidazolium triphenylborane, and triethanolamine triphenylphosphine, for example.
The curing accelerator may be, for example, an imidazole such as an alkyl-substituted imidazole or benzimidazole. The imidazole compound tends to have an activation temperature lower than that of the borate and borane compounds. Therefore, the imidazole-containing composite powder is easily cured at a lower temperature in a short time than the composite powder containing a borate or borane compound. In other words, in the imidazole-containing composite powder, the curing of the semi-cured product of the epoxy resin as a solid residue is likely to proceed with the molding or storage of the composite powder. Therefore, imidazoles are suitable as a curing accelerator when a molded article is cured in a short time. The composite powder may contain, as the imidazole-based curing accelerator, at least one selected from the group consisting of, for example, 1-cyanoethyl-2-undecylimidazole, 2-heptadecylimidazole, 2-ethyl-4-methylimidazole and 1-cyanoethyl-2-phenylimidazole. As the commercially available product of the imidazole-based curing accelerator, at least one selected from the group consisting of 2MZ-H, C11Z, C Z, 1,2DMZ, 2E4MZ, 2PZ-PW, 2P4MZ, 1B2PZ, 2MZ-CN, C11Z-CN, 2E4MZ-CN, 2PZ-CN, C11Z-CNS, 2P4MHZ, TPZ and SFZ (the above is a trade name manufactured by Shikoku Kagaku K.K.) can be used, for example.
The amount of the curing accelerator to be blended is not particularly limited as long as the curing accelerator can obtain the curing acceleration effect. However, from the viewpoint of improving curability and fluidity of the epoxy resin when it absorbs moisture, the amount of the curing accelerator is preferably 0.1 to 30 parts by mass, and 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 parts by mass or more and 5 parts by mass or less with respect to the total mass of the epoxy resin and the curing agent (for example, phenol resin). When the 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 is 30 parts by mass or less, the storage stability of the composite powder is easily improved. However, the effects of the present invention can be obtained even when the compounding amount and content of the curing accelerator are out of the above ranges.
The composite powder may comprise a wax. The composite powder may contain wax as part of the solid component residue.
As the content of the solid residue in the composite powder is larger, the proportion of the epoxy resin (uncured epoxy resin) softened or liquefied by heating is smaller, and the composite powder tends to be less fluidized. However, when the composite powder contains wax, the wax is liquefied by heating the composite powder at a temperature around the melting point of the wax, and the entire composite powder can have excellent fluidity derived from the wax. The ratio of the wax in the composite powder by volume may be, for example, 1 vol% or more and 10 vol% or less. When the volume ratio of the wax in the composite powder is within the above numerical range, it is easy to achieve both of the physical properties (for example, insulation property, magnetic permeability, electric field shielding value, residual magnetic flux density, and the like) derived from the metal element-containing powder and the epoxy resin and the excellent fluidity of the composite powder. The wax contained in the composite powder may be, for example, a powder (wax powder).
A part or all of the curing accelerator may be dissolved in the wax. By heating the composite powder, the wax in the composite powder liquefies, and the curing accelerator dissolved in the wax accelerates the curing of the resin composition. By dissolving the curing accelerator in the wax, thermal deterioration of the composite powder and the web formed of the composite powder with the passage of time can be easily suppressed.
The wax may be at least one of a fatty acid such as a higher fatty acid and a fatty acid ester. The composite powder may contain a variety of waxes.
The wax is selected from fatty acids such as montanic acid, stearic acid, 12-hydroxystearic acid, lauric acid, etc., or esters thereof; fatty acid salts such as zinc stearate, calcium stearate, barium stearate, aluminum stearate, magnesium stearate, calcium laurate, zinc linoleate, calcium ricinoleate, zinc 2-ethylhexanoate and the like; fatty amides such as stearamide, oleamide, erucamide, behenamide, palmitamide, lauramide, hydroxycysteine amide, methylenebisstearamide, ethylenebisstearamide, ethylenebislauramide, distearyladipamide, ethylenebisoleamide, dioleyladipamide, N-stearylstearamide, N-oleylstearamide, N-stearylerucamide, hydroxymethylstearamide, and hydroxymethylbehenamide; fatty acid esters such as butyl stearate; alcohols such as ethylene glycol and stearyl alcohol; polyethers composed of polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and modified products thereof; silicones such as silicone oil and silicone grease (silicone grease); fluorine compounds such as fluorine-based oils, fluorine-based greases, and fluorine-containing resin powders; and waxes such as paraffin wax, polyethylene wax, amide wax, polypropylene wax, ester wax, carnauba wax, and microwax; at least one of (a).
As a commercial product of montanic acid wax, at least one selected from the group consisting of Licowax E, licowax OP, licoub E, and licoub WE 40 (trade name of Clariant Chemicals, supra) can be used. As a commercially available stearic acid wax, at least either of Lunac S-50V (titer: 56 ℃) and Lunac S-90V (melting point: 68 ℃) available from Kao corporation can be used. As a commercially available product of polyethylene wax, at least one selected from the group consisting of Licolub H12, licowax PE520, and Licowax PED191 (hereinafter, referred to as a trade name of Clariant Chemicals). As a commercially available product of the amide wax, at least one of Licolub FA1 (trade name manufactured by Clariant Chemicals Co., ltd.) and DISPARLON 6650 (trade name manufactured by Nanba Kabushiki Kaisha) can be used. The wax may be appropriately selected depending on the fluidity, mold releasability, temperature and pressure at the time of molding, and the design requirements of the composite powder such as melting point, dropping point and melt viscosity of the wax. From the viewpoints of fluidity, mold releasability, temperature and pressure at the time of molding, and melting point of the wax, it is particularly preferable that the composite powder contains at least one of Lunac S-50V and Lunac S-90V.
The average particle diameter of the composite powder is not particularly limited, and may be, for example, 100 μm or more and 2000 μm or less. The average particle diameter of the metal-element-containing powder contained in the composite powder is not particularly limited, and may be, for example, 1 μm or more and 300 μm or less. The average particle diameter of the wax powder is not particularly limited, and may be, for example, 10 μm or more and 2000 μm or less. The average particle diameter can be measured by a particle size distribution meter, for example. The shape of each particle constituting the composite powder is not limited, and may be, for example, a spherical shape, a flat shape, a prismatic shape, or a needle shape.
The composite powder of the present embodiment can have excellent fluidity, and therefore can be easily molded into a desired shape. In addition, when the composite powder contains wax powder, the wax also functions as a release agent, and therefore, the composite powder can be easily separated from the mold without damaging the molded article formed from the composite powder. In addition, when the composite powder of the present embodiment is used to form a molded body, burrs are less likely to be formed. For these reasons, the composite powder of the present embodiment is easily used for transfer molding (transfer molding). Transfer molding is one of injection molding methods of thermosetting resins. Transfer molding may be in other words press molding. The transfer molding may include: the method includes a step of heating and fluidizing the composite powder in a heating chamber, and a step of supplying (pressing) the fluidized composite powder from the heating chamber into a mold through a casting runner. The transfer molding may include: the method includes a step of heating the composite powder in the heating chamber to fluidize the composite powder, and a step of supplying the fluidized composite powder from the heating chamber into the plunger and supplying (pressing) the composite powder from the plunger into the mold through the runner. The composite powder of the present embodiment exhibits excellent fluidity under heating, and therefore, flows easily without interruption (without inclusion of air bubbles) in a thin runner, and is easily uniformly (without forming spots) filled in a space (cavity) in a mold. As a result, a molded body with few defects such as voids and burrs can be formed from the composite powder. Therefore, the productivity of the molded article is improved by the present invention. The method of molding the composite powder is not limited to the transfer molding, and may be, for example, extrusion molding. A web formed from the composite powder may also be used as the starting material for the above-described transfer molding.
As described below, the composite powder of the present embodiment can be used for a magnetic core. For example, in the case of manufacturing an inductor by transfer molding, the transfer molding may include: the method includes a step of supplying fluidized composite powder into a mold, a step of embedding a part or the whole of the air-core coil in the composite powder in the mold, and a step of solidifying the composite powder embedded with the air-core coil. Since the composite powder of the present embodiment has excellent fluidity, the composite powder can be easily and uniformly filled into the air-core coil, and a part or the whole of the surface of the air-core coil can be easily and uniformly covered with the composite powder. The composite powder filled in the air-core coil becomes a magnetic core of the inductor by curing, and is firmly adhered to the air-core coil. As a result, an inductor having high mechanical strength is obtained.
The use of the composite powder of the present embodiment is not limited to the magnetic core of an inductor. The composition or combination of the metal element-containing powder contained in the composite powder enables the electromagnetic properties, thermal conductivity, and other physical properties of the composite powder to be freely controlled, and the composite powder can be used for various industrial products or raw materials thereof. Industrial products produced using the composite powder may be, for example, automobiles, medical devices, electronic devices, electrical devices, information communication devices, household electric appliances, acoustic devices, and general industrial devices. For example, in the case where the composite powder contains soft magnetic powder such as Fe — Si — Cr based alloy or ferrite as the metal element-containing powder, the composite powder can be used as a material (e.g., magnetic core) of the above-described inductor (e.g., EMI filter) or transformer. In the case where the composite powder contains a permanent magnet as the metal element-containing powder, the composite powder can be used as a raw material of the bonded magnet. In the case where the composite powder contains iron and copper as the metal element-containing powder, a molded body (e.g., a sheet) formed of the composite powder can be used as the electromagnetic wave shielding material.
The "resin composition" described below is a component containing at least an epoxy resin and a curing agent, and is a component that may contain other resins, curing accelerators, and additives as needed, and is defined as the remaining component (nonvolatile component) excluding the organic solvent and the metal element-containing powder from the composite powder. The additive means the remaining components of the resin composition excluding the resin, the curing agent and the curing accelerator. The additives are, for example, coupling agents or flame retardants. The resin composition may contain a wax as an additive. As described below, the composite powder includes a metallic element-containing powder and a resin composition. A part or the whole of the surface of each particle (metal element-containing powder) constituting the metal element-containing powder may be covered with the resin composition. A part or the whole of the surface of the metal element-containing powder may be covered with the resin composition and the wax powder.
The resin composition functions as a binder (binder) for the metal element-containing powder, and imparts mechanical strength to a molded body formed from the composite powder. For example, the resin composition contained in the composite powder is filled between the metal element-containing powders when the composite powder is molded under high pressure using a mold, and the metal element-containing powders are bonded to each other. By curing the resin composition in the molded body, the cured product of the resin composition more firmly bonds the particles constituting the metal element-containing powder to each other, and the mechanical strength of the molded body is improved.
The resin composition contains at least an epoxy resin as a thermosetting resin. When the composite powder contains an epoxy resin having relatively excellent fluidity in the thermosetting resin, the fluidity, storage stability and moldability of the composite powder are improved. However, the composite powder may contain other resins in addition to the epoxy resin as long as the effects of the present invention are not hindered. For example, the resin composition may include at least one of a phenol resin and a polyamideimide resin as the thermosetting resin. When the resin composition contains both an epoxy resin and a phenol resin, the phenol resin can function as a curing agent for the epoxy resin. The resin contained in the composite powder may be only a thermosetting resin, and the thermosetting resin may be only an epoxy resin, or only an epoxy resin and a phenolic resin. The resin composition may include 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, and polyethylene terephthalate. The resin composition may contain both a thermosetting resin and a thermoplastic resin. The resin composition may contain a silicone resin.
The content of the resin composition in the composite powder may be 0.2 to 10% by mass, and more preferably 4 to 6% by mass, based on the mass of the entire composite powder (for example, the total mass of the metal element-containing powder and the resin composition). When the content of the resin composition is within the above range, moldability of each of the composite powder and the web can be easily achieved at the same time.
The epoxy resin is excellent in fluidity in the thermosetting resin, and therefore the resin composition preferably contains the epoxy resin. The epoxy resin may be, for example, a resin having 2 or more epoxy groups in 1 molecule.
The epoxy resin may be at least one selected from the group consisting of a stilbene type epoxy resin, a diphenylmethane type epoxy resin, a sulfur atom containing type epoxy resin, a novolak type epoxy resin, a dicyclopentadiene type epoxy resin, a salicylaldehyde type epoxy resin, a copolymer type epoxy resin of naphthols and phenols, an epoxide of an aralkyl type phenol resin, a bisphenol type epoxy resin, a glycidyl ether type epoxy resin of alcohols, a glycidyl ether type epoxy resin of a p-xylene and/or m-xylene modified phenol resin, a glycidyl ether type epoxy resin of a terpene modified phenol resin, a cyclopentadiene type epoxy resin, a glycidyl ether type epoxy resin of a polycyclic aromatic ring modified phenol resin, a glycidyl ether type epoxy resin of a naphthalene ring containing phenol resin, a glycidyl ester type epoxy resin, a glycidyl or methylglycidyl type epoxy resin, an alicyclic epoxy resin, a halogenated phenol novolak type epoxy resin, a hydroquinone type epoxy resin, a trimethylolpropane type epoxy resin, and a linear aliphatic epoxy resin obtained by oxidizing an olefin bond with peracetic acid or the like.
From the viewpoint of excellent fluidity, the epoxy resin may be at least one selected from the group consisting of biphenyl-type epoxy resins, o-cresol novolac-type epoxy resins, phenol novolac-type epoxy resins, salicylic novolac-type epoxy resins, and naphthol novolac-type epoxy resins.
The epoxy resin may be a crystalline epoxy resin. Although the molecular weight of the crystalline epoxy resin is low, the crystalline epoxy resin has a high melting point and is excellent in fluidity. The crystalline epoxy resin (epoxy resin having high crystallinity) may be at least one selected from, for example, a hydroquinone-type epoxy resin, a bisphenol-type epoxy resin, a thioether-type epoxy resin, and a biphenyl-type epoxy resin. Commercially available products of the crystalline epoxy resin include, for example, EPICLON 860, EPICLON 1050, EPICLON 1055, EPICLON 2050, EPICLON 3050, EPICLON 4050, EPICLON 7050, EPICLON HM-091, EPICLON HM-101, EPICLON-730A, EPICLON N-740, EPICLON-770, EPICLON-775, EPICLON-865, EPICLON HP-4032D, EPICLON HP-7200L, EPICLON HP-7200H, EPICLON HP-7200HHH, EPLON HP-4700, EPICLON HP-4710, EPICLON HP-4770, EPICLON HP-5000, EPICLON LON HP-6000, and EPICLON HP-6000, trade name of the trade name of EPICLON HP-4032 or more (trade name: EPICLON 2) at least one of 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 (trade name manufactured by Nippon Kagaku corporation), YX-4000H, YL4121H and YX-8800 (trade name manufactured by Mitsubishi chemical corporation).
The resin composition may contain one of the above epoxy resins. The resin composition may contain a plurality of epoxy resins as described above.
The curing agent is classified into a curing agent that cures an epoxy resin in a range from low temperature to room temperature, and a heat-curing type curing agent that cures an epoxy resin with heating. Curing agents that cure epoxy resins in the range from low temperatures to room temperature are, for example, aliphatic polyamines, polyaminoamides, polythiols and the like. Examples of the heat-curable curing agent include aromatic polyamine, acid anhydride, phenol novolac resin, and Dicyandiamide (DICY).
When a curing agent that cures an epoxy resin at a temperature in the range from low temperature to room temperature is used, the glass transition temperature of a cured product of the epoxy resin tends to be low, and the cured product of the epoxy resin tends to be flexible. As a result, the molded body made of the composite powder is also easily softened. On the other hand, from the viewpoint of improving the heat resistance of the molded article, the curing agent is preferably a heat-curable curing agent, more preferably a phenol resin, and still more preferably a phenol novolac resin. In particular, by using a phenol novolac resin as a curing agent, a cured product of an epoxy resin having a high glass transition temperature can be easily obtained. As a result, the heat resistance and mechanical strength of the molded article are easily improved.
The phenol resin may be, for example, at least one selected from the group consisting of an aralkyl type phenol resin, a dicyclopentadiene type phenol resin, a salicylaldehyde type phenol resin, a novolak type phenol resin, a copolymerized type phenol resin of a benzaldehyde type phenol and an aralkyl type phenol, a p-xylene and/or m-xylene modified phenol resin, a melamine modified phenol resin, a terpene modified phenol resin, a dicyclopentadiene type naphthol resin, a cyclopentadiene modified phenol resin, a polycyclic aromatic ring modified phenol resin, a biphenyl type phenol resin, and a triphenylmethane type phenol resin. The phenol resin may be a copolymer composed of 2 or more of the above. As a commercially available product of the phenol resin, TAMANOL 758 manufactured by Mikan chemical industries, or HP-850N manufactured by Hitachi chemical Co., ltd.
The phenol novolac resin may be, for example, a resin obtained by condensing or co-condensing a phenol and/or a naphthol with an aldehyde under an acidic catalyst. The phenol constituting the phenol novolac resin may be at least one selected from the group consisting of phenol, cresol, xylenol, resorcinol, catechol, bisphenol a, bisphenol F, phenylphenol, and aminophenol, for example. The naphthol constituting the phenol novolac resin may be at least one selected from α -naphthol, β -naphthol and dihydroxynaphthalene, for example. The aldehyde constituting the phenol novolac resin may be at least one selected from formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde, and salicylaldehyde, for example.
The curing agent may be, for example, a compound having 2 phenolic hydroxyl groups in 1 molecule. The compound having 2 phenolic hydroxyl groups in 1 molecule may be, for example, at least one selected from resorcinol, catechol, bisphenol a, bisphenol F, and substituted or unsubstituted biphenol.
The resin composition may contain one of the above-mentioned phenol resins. The resin composition may include a plurality of the phenolic resins described above. The resin composition may contain one of the above curing agents. The resin composition may contain a plurality of curing agents as 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 is preferably 0.5 to 1.5 equivalents, more preferably 0.9 to 1.4 equivalents, and still more preferably 1.0 to 1.2 equivalents, to 1 equivalent of the epoxy group in the epoxy resin. When the ratio of the active groups in the curing agent is less than 0.5 equivalent, the OH amount per unit weight of the cured epoxy resin decreases, and the curing rate of the resin composition (epoxy resin) decreases. In addition, when the ratio of the active groups in the curing agent is less than 0.5 equivalent, the glass transition temperature of the resulting cured product is lowered, or a sufficient elastic modulus of the cured product cannot be obtained. On the other hand, when the ratio of the active groups in the curing agent exceeds 1.5 equivalents, the mechanical strength of the molded article formed of the composite powder after curing tends to be lowered. However, even when the ratio of the active groups in the curing agent is outside the above range, the effects of the present invention can be obtained.
The coupling agent improves the adhesion between the resin composition and the metal element-containing powder, and improves the flexibility and mechanical strength of the molded article formed from the composite powder. The surface of each of the metal element-containing particles contained in the metal element-containing powder may be treated with a coupling agent. The coupling agent may be at least one selected from silane-based compounds (silane coupling agents), titanium-based compounds, aluminum compounds (aluminum chelates), and aluminum/zirconium-based compounds, for example. The silane coupling agent may be at least one selected from epoxy silane, mercapto silane, amino silane, alkyl silane, ureido silane, acid anhydride silane, and vinyl silane, for example. Particularly preferred is an aminophenyl-based silane coupling agent. The composite powder may contain one or more of the above coupling agents.
The composite powder may contain a flame retardant for the purpose of environmental safety, recyclability, moldability and low cost of the composite powder. The flame retardant may be 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, for example. The composite powder may contain one or more of the above flame retardants.
The metal element-containing powder may contain, for example, at least one selected from the group consisting of simple metals, alloys, and metal compounds. The metal element-containing powder may be composed of at least one selected from the group consisting of simple metals, alloys, and metal compounds, for example. The alloy may contain at least one selected from a solid solution, a eutectic, and an intermetallic compound. The alloy may be, for example, stainless steel (e.g., fe-Cr alloy, fe-Ni-Cr alloy, etc.). The metal compound may be an oxide such as ferrite. The metal element-containing powder may contain one metal element or a plurality of metal elements. The metal element contained in the metal-containing powder may be, for example, a base metal element, a noble metal element, a transition metal element or a rare earth element. The composite powder may contain one kind of metal-containing element powder or may contain a plurality of kinds of metal-containing element powders.
The metal element-containing powder is not limited to the above composition. The metal element contained in the metal-containing powder may be at least one metal element 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), for example. The metal element-containing powder may contain an element other than the metal element. The elemental metal-containing powder may contain, for example, oxygen (O), beryllium (Be), phosphorus (P), boron (B), or silicon (Si). The metal element-containing powder may be a magnetic powder. The metallic element-containing powder may be a soft magnetic alloy or a ferromagnetic alloy. <xnotran> Fe-Si , fe-Si-Al ( ), fe-Ni ( ), fe-Cu-Ni ( ), fe-Co ( ), fe-Cr-Si ( ), nd-Fe-B ( ), sm-Co ( ), sm-Fe-N ( ), al-Ni-Co ( ) . </xnotran> The ferrite may be, for example, spinel ferrite, hexagonal ferrite, or garnet ferrite. The metal-containing powder may 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-containing powder may contain one of the elements and the composition, or may contain a plurality of the elements and the composition.
The metal element-containing powder may also be elemental Fe. The metallic element-containing powder may be an alloy containing iron (Fe-based alloy). The Fe-based alloy may be, for example, an Fe-Si-Cr-based alloy or an Nd-Fe-B-based alloy. The elemental metal-containing powder may be at least one of an amorphous iron powder and a carbonyl iron powder. In the case where the first powder contains at least either of a simple substance of Fe and an Fe-based alloy as the metal element-containing powder, a compact having a high space factor and excellent magnetic characteristics can be easily produced from the composite powder. The metallic element-containing powder may also be an Fe amorphous alloy. As a commercial product of the Fe amorphous alloy powder, at least one selected from AW2-08, KUAMET-6B2 (trade name of EPSON ATMIX Co., ltd., the above), DAP MS3, DAP MS7, DAP MSA10, DAP PB, DAP PC, DAP MKV49, DAP 410L, DAP L, DAP HYB series (trade name of DATON Special Steel Co., ltd., the above), 45D, MM28D, MH D, and MH20D (trade name of Kobe Steel Co., ltd., the above) can be used, for example.
The content of the metal element-containing powder in the composite powder may be 92.0 mass% or more and 99.0 mass% or less. When the content of the metal element-containing powder is within the above range, the fluidity, storage stability and moldability of the composite powder are easily improved.
The particle diameter of the metal-containing powder may satisfy the following condition 1 to 5. However, even when the conditions 1 to 5 are not satisfied, the effects of the present invention can be obtained.
< condition 1> the particle size distribution of the metal-element-containing powder has two peaks, a1 st peak and a 2 nd peak, and the particle size of the 1 st peak is larger than that of the 2 nd peak.
< Condition 2> the particle size of the 2 nd peak is 1/2 or less, preferably 1/3 or less of the particle size of the 1 st peak. However, the particle diameter of the 2 nd peak is 1/10 or more of the particle diameter of the 1 st peak. As the particle diameter of peak 2 decreases, the surface area of the particle having the particle diameter of peak 2 increases, and the TI value (thixotropic index) increases. As the TI value increases, the fluidity of the entire composite powder may decrease.
< condition 3> the ratio I2/I1 (presence ratio) of the intensity I2 of the 2 nd peak to the intensity I1 of the 1 st peak is 0.2 or more and 0.6 or less, preferably 0.25 or more and 0.4 or less. For example, I2/I1 is about 0.3.
< condition 4> the particle diameter of the 1 st peak was dispersed substantially at the center of 22 μm.
< Condition 5> D90% of the particle size distribution was approximately 60 μm or less.
In the production of the composite powder, the metal element-containing powder and the resin composition are mixed while heating. For example, the metal element-containing powder and the resin composition may be kneaded by a kneader or a stirrer while being heated. By heating and mixing the metal element-containing powder and the resin composition, the resin composition adheres to a part or the whole of the surface of the metal element-containing particles to cover the metal element-containing particles, and a part or the whole of the epoxy resin in the resin composition becomes a semi-cured product. As a result, a composite powder was obtained. A wax powder may be further added to the powder obtained by heating and mixing the metal element-containing powder and the resin composition, thereby obtaining a composite powder. The resin composition and the wax powder may be mixed in advance. The content of the solid content residue in the composite powder can be controlled by the mass of the metal element-containing particles mixed with the resin composition and the mass of the semi-cured product of the epoxy resin produced during heating and mixing with the metal element-containing powder. The quality of the semi-cured product of the epoxy resin can be controlled by the temperature, heating time, and selection of the curing agent and the curing accelerator during heating and mixing.
In the kneading, a metal element-containing powder, a curing agent such as an epoxy resin or a phenol resin, a curing accelerator, and a coupling agent may be kneaded in a tank. Or after the metal element-containing powder and the coupling agent are put into the tank and mixed, the epoxy resin, the curing agent and the curing accelerator are put into the tank, and the raw materials in the tank are mixed. After the epoxy resin, the curing agent, and the coupling agent are kneaded in the tank, the curing accelerator may be put into the tank, and the raw materials in the tank may be further kneaded. Alternatively, a mixed powder of an epoxy resin, a curing agent and a curing accelerator (resin mixed powder) may be prepared in advance, and then the metal element-containing powder and the coupling agent may be kneaded to prepare a metal mixed powder, and then the metal mixed powder may be kneaded with the resin mixed powder.
The kneading time by the kneader depends on the volume of the tank and the production amount of the composite powder, and is, for example, preferably 5 minutes or longer, more preferably 10 minutes or longer, and still more preferably 20 minutes or longer. The kneading time by the kneader is preferably 120 minutes or less, more preferably 60 minutes or less, and still more preferably 40 minutes or less. When the kneading time is less than 5 minutes, kneading is insufficient, moldability of the composite powder is impaired, and the degree of curing of the composite powder varies. When the kneading time exceeds 120 minutes, for example, curing of the resin composition (e.g., epoxy resin and phenol resin) in the tank proceeds, and the flowability and moldability of the composite powder are easily impaired. When the raw material in the tank is kneaded by a kneader while being heated, the heating temperature may be, for example, a temperature at which a prepreg of the epoxy resin (the epoxy resin in the B stage) is produced and the production of a cured epoxy resin (the epoxy resin in the C stage) is suppressed. The heating temperature may be a temperature lower than the activation temperature of the curing accelerator. The heating temperature is, for example, preferably 50 ℃ or higher, more preferably 60 ℃ or higher, and still more preferably 80 ℃ or higher. The heating temperature is preferably 150 ℃ or lower, more preferably 120 ℃ or lower, and still more preferably 110 ℃ or lower. When the heating temperature is within the above range, the resin composition in the tank is softened and easily covers the surface of the metal element-containing particles, a semi-cured product of the epoxy resin is easily produced, and complete curing of the epoxy resin during kneading is easily suppressed.
The web can be formed by filling the composite powder into a predetermined mold and molding by pressing. The shape and size of the web are not particularly limited. For example, in the case where the web is cylindrical, the diameter of the web may be 5mm or more, and the height (length) of the web may be 5mm or more. The web forming pressure is, for example, preferably 500MPa or more, more preferably 1000MPa or more, and further preferably 2000MPa or more.
When the molded body is produced by transfer molding of the composite powder, the molding pressure may be 500 to 2500MPa. The higher the molding pressure, the higher the mechanical strength of the molded article. The pressure of the molded article may be 1400 to 2000MPa from the viewpoint of mass productivity of the molded article and the life of the mold. The density of the molded article produced by transfer molding is preferably 75% or more and 86% or less, and more preferably 80% or more and 86% or less, with respect to the true density of the composite powder. By setting the density of the molded article to 75% or more and 86% or less, an inductor having excellent magnetic properties and high mechanical strength can be produced.
In the case of manufacturing an inductor by transfer molding of the composite powder, the glass transition temperature of a resin cured product formed by curing the resin composition in the molded body is preferably 150 ℃ or higher, and more preferably 160 ℃ or higher. By setting the glass transition temperature of the cured resin to 150 ℃ or higher, an inductor can be produced whose mechanical strength is less likely to decrease even in a high-temperature and severe environment. The glass transition temperature is a temperature at which tan δ (loss tangent) reaches a peak (maximum) in the dynamic viscoelasticity measurement of the resin composition.
The compressive strength of the inductor manufactured by transfer molding at a temperature of 150 ℃ is preferably 100MPa or more, more preferably 150MPa, and still more preferably 200MPa or more. By setting the compressive strength to 100MPa or more, an inductor having high mechanical strength even at high temperatures can be manufactured.
Examples
The present invention will be described in further detail below with reference to examples and comparative examples, but the present invention is not limited to these examples at all.
(example 1)
[ preparation of composite powder ]
65.6 parts by mass of a biphenyl type epoxy resin, 24.4 parts by mass of a phenol novolac resin (curing agent), 0.66 part by mass of tetra-n-butylphosphonium tetraphenylborate (borate-based curing accelerator), and 4.8 parts by mass of montanic acid ester (wax powder) were charged into a plastic container. These raw materials were mixed in a plastic container for 10 minutes, thereby preparing a resin mixture.
As the biphenyl type epoxy resin, NC-3000H (epoxy equivalent 291, melting point 70 ℃ C.) manufactured by Nippon chemical Co., ltd was used.
As the phenol novolak resin, HP-850N (hydroxyl equivalent: 108, melting point: 83 ℃) available from Hitachi chemical Co., ltd was used.
As tetra-n-butylphosphonium tetraphenylborate, PX-4PB (molecular weight: 579, melting point 230 ℃ C.) manufactured by Nippon chemical industries, ltd.
Licowax E (mold release agent, melting point 82 ℃ C.) manufactured by Clariant corporation was used as the montanic acid ester.
992.2 parts by mass of amorphous iron powder and 811.8 parts by mass of carbonyl iron powder were uniformly mixed for 5 minutes by a pressure twin-screw kneader (5L, manufactured by Spindel, japan) to prepare metal element-containing powder. 9.5 parts of 3-glycidoxypropyltrimethoxysilane (silane coupling agent) was added to the metal-containing powder in the twin-screw kneader. Subsequently, the contents of the twin-screw kneader were heated to 90 ℃ and mixed for 10 minutes while maintaining the temperature. Next, the resin mixture was added to the contents of the twin-screw kneader, and the contents were melted and kneaded for 15 minutes while maintaining the temperature of the contents at 120 ℃. "120 ℃ C" corresponds to "melt kneading temperature" in the following table. "15 minutes" corresponds to "melt-kneading time" in the following table. After the kneaded material obtained by the above melting and kneading is cooled to room temperature, the kneaded material is pulverized with a hammer until the kneaded material has a predetermined particle size. The term "melt" as used herein means that at least a part of the resin composition in the contents of the twin-screw kneader is melted. The metal-containing powder in the composite powder is not melted in the preparation process of the composite powder.
As the amorphous iron powder, 6B2 (average particle size 25 μm) manufactured by Epson Atmix was used.
As the carbonyl iron powder, SQ-I (average particle diameter 5 μm) manufactured by BASF Japan was used.
As 3-glycidoxypropyltrimethoxysilane, KBM-403 (molecular weight: 236) available from shin-Etsu chemical Co., ltd was used.
By the above method, the composite powder of example 1 was prepared. The content of the metal element-containing powder in the composite powder was 94.0 mass%.
[ measurement of the content of solid residue ]
50ml of Methyl Ethyl Ketone (MEK) was charged into a plastic container having a capacity of 100 ml. Next, 10g of the composite powder was added to MEK in a plastic container, and the contents of the plastic container were stirred at room temperature for 60 minutes. A mixing rotor (VMR-5R) manufactured by AS ONE was used for stirring. The rotational speed of the mixing rotor was set at 80rpm. After stirring, the solid content residue in MEK was taken out of the plastic container, and dried under reduced pressure at room temperature for 1.0 hour. Vacuum drying was performed using a vacuum dryer (AV-310) manufactured by AS ONE. The solid residue of example 1 was obtained through the above procedure. The mass of the solid residue after drying was measured. The content (unit: mass%) of the solid residue in the composite powder of example 1 was calculated based on the following formula (a). The content of the solid content residue in example 1 is shown in table 1 below.
C SR ＝(M SR /M C )×100 (a)
C in the numerical formula (a) SR Is the content of solid content residue in the composite powder. M SR The mass (unit: g) of the dried solid residue was determined. M C Is the mass (unit: g) of the composite powder before addition to MEK. M of example 1 C 10g as described above.
[ evaluation of fluidity ]
50g of the composite powder was charged into a transfer tester, and the spiral flow amount (unit: mm) of the composite powder was measured at a mold temperature (molding temperature) of 165 ℃, an injection pressure of 6.9MPa, and a molding time of 180 seconds. The spiral flow rate is a length over which the softened or liquefied composite powder flows in a spiral curve (archimedean spiral) groove formed in the mold. That is, the spiral flow amount refers to the flow distance of the composite powder after softening or liquefaction. The more easily the composite powder softened or liquefied under heating flows, the greater the amount of spiral flow. That is, the composite powder having excellent fluidity has a large spiral flow amount. A transfer molding machine manufactured by T-Marushichi was used as a transfer tester. As the mold, a mold for spiral flow measurement based on ASTM D3123 was used. The spiral flow amount (initial spiral flow amount) of example 1 is shown in the following table 1.
[ evaluation of storage stability ]
The composite powder was stored in a refrigerator at 5 ℃ for 3 months. The spiral flow amount (unit: mm) of the composite powder after storage was measured by the method described above. The spiral flow amount after storage in example 1 is shown in table 1 below. The reduction ratio (unit:%) of the spiral flow amount in example 1 was calculated based on the following formula (b). The reduction rate of the spiral flow amount in example 1 is shown in table 1 below. The smaller the reduction rate of the spiral flow amount, the more excellent the storage stability of the composite powder.
Rs＝{(L1-L2)/L1}×100 (b)
L1 in the formula (b) is the initial spiral flow amount described above. L2 is the spiral flow amount after the storage.
[ evaluation of curing State ]
The molded article in a spiral curve shape prepared at the initial spiral flow measurement was touched with a hand to evaluate the cured state of the molded article. The cured state of the molded article of example 1 is shown in table 1 below. A, B, C and D in the following table indicate the hardness of the molded article. The relationship between the hardness A, B, C and D is as follows. The molded article having a hardness of A has excellent moldability.
A>B>C>D
(examples 2 to 12)
In examples 2 to 12, the compositions shown in table 1 below were used as raw materials of the composite powder. The mass ratio (unit: part by mass) of each composition used in examples 2 to 12 is a value shown in table 1 below. The melt-kneading temperature and the melt-kneading time in each of examples 2 to 12 were as shown in table 1 below. Except for these matters, composite powders of examples 2 to 12 were prepared in the same manner as in example 1. The measurement and evaluation of the composite powders of examples 2 to 12 were carried out by the same method as in example 1. The results of measurement and evaluation of each of examples 2 to 12 are shown in table 1 below.
Comparative examples 1 to 6
In comparative examples 1 to 6, the compositions shown in table 2 below were used as raw materials of the composite powder. The mass ratio (unit: part by mass) of each composition used in comparative examples 1 to 6 is a value shown in table 2 below. The melt-kneading temperature and the melt-kneading time of each of comparative examples 1 to 6 were values shown in table 2 below. Except for these matters, composite powders of comparative examples 1 to 6 were prepared by the same method as in example 1. The measurement and evaluation of the composite powders of comparative examples 1 to 6 were carried out by the same method as in example 1. The results of measurement and evaluation of each of comparative examples 1 to 6 are shown in table 2 below. However, as described later, the spiral flow amount of each of comparative examples 4 to 6 could not be measured.
YX4000H shown in the following Table is a biphenyl type epoxy resin (having an epoxy equivalent of 192 and a melting point of 105 ℃ C.) manufactured by Mitsubishi chemical corporation.
EPPN-502H shown in the following table is a salicylaldehyde novolac resin (epoxy equivalent weight 171, melting point 66 ℃ C.) made by Nippon Kagaku K.K.
KA1165 shown in the following Table is a cresol novolak resin manufactured by DIC corporation (hydroxyl equivalent: 119, melting point: 122 ℃ C.).
C11Z-CN shown in the following Table is 1-cyanoethyl-2-undecylimidazole, and is an imidazole-based curing accelerator (molecular weight: 275, melting point 50 ℃ C.) manufactured by Shikoku Kabushiki Kaisha.
< measurement result of solid residue >
In each of examples 1 to 12, a borate-based curing accelerator was used, and the melt kneading temperature/time was 120 ℃/15 minutes or 90 ℃/35 minutes. In each of examples 1 to 12, the content of the solid content residue was 98.5 mass% or more and 99.5 mass% or less. On the other hand, in comparative examples 1 to 3, the imidazole curing accelerator was used, and the melt kneading temperature/time was 90 ℃/15 minutes. In any of comparative examples 1 to 3, the content of the solid content residue was less than the target value (98.5 mass%). In comparative examples 4 to 6, borate-based curing accelerators were used, and the melt kneading temperature/time was 90 ℃/15 minutes. The solid content of the residue in each of comparative examples 4 to 6 was less than the target value (98.5 mass%) and less than that in any of examples 1 to 12 and comparative examples 1 to 3. In comparative examples 4 to 6, it was found that about 6.0 mass% of the resin composition contained in the composite powder was mostly dissolved in MEK.
< evaluation result of cured State of molded article >
It was confirmed that the molded articles of examples 1 to 12 were all sufficiently hard. On the other hand, it is clear that the molded articles of comparative examples 1 to 3 are all softer and less cured than those of examples 1 to 12. It is also clear that the molded articles of comparative examples 4 to 6 are very soft and have very insufficient curing compared to examples 1 to 12 and comparative examples 1 to 3.
< evaluation results of storage stability >
It was confirmed that the reduction rate of the spiral flow amount in examples 1 to 12 was not more than the target value (10%). On the other hand, it was confirmed that the reduction rate of the spiral flow amount in comparative examples 1 to 3 was extremely higher than the target value. In any of comparative examples 4 to 6, since the composite powder was too soft during transfer molding, neither the initial spiral flow amount nor the spiral flow amount after storage could be measured.
Industrial applicability
The composite powder and the composite powder of the present invention are excellent in fluidity and storage stability, and have high industrial values.
Claims (8)
1. A composite powder comprising a metal element-containing powder and a resin composition which is a nonvolatile component in the composite powder comprising an epoxy resin, a curing agent and a curing accelerator, wherein,
the content of a solid residue remaining after the composite powder is dissolved in a ketone solvent is 98.5 to 99.5 mass%,
the solid content residue contains the semi-cured product of the epoxy resin and the metal element-containing powder,
the content of the metal element-containing powder in the composite powder is 92.0 mass% or more and 96.0 mass% or less,
the curing accelerator is at least one of borate and borane compound.
2. The composite powder according to claim 1,
the borate is represented by the following general formula (1),
X + B - (R) 4 (1)
in the general formula (1), X is at least one selected from alkyl phosphonium salt, aryl phosphonium salt, imidazole salt, salt of imidazole derivative, tertiary amine salt and quaternary ammonium salt, B is boron, and R is at least one selected from alkyl, aryl and fluorine group.
3. The composite powder according to claim 1,
the borane compound is represented by the following general formula (2),
Y·B(R) 3 (2)
in the general formula (2), Y is at least one selected from alkyl phosphine, aryl phosphine, imidazole derivative and tertiary amine, B is boron, and R is at least one selected from alkyl, aryl and fluoro.
4. A composite powder according to any one of claims 1 to 3 comprising a wax.
5. The composite powder according to any one of claims 1 to 3,
the metal-containing powder is at least one selected from the group consisting of Sm-Co alloy powder, fe-Co alloy powder, sm-Fe-N alloy powder, ferrite powder, amorphous iron powder and carbonyl iron powder.
6. The composite powder according to any one of claims 1 to 3,
the epoxy resin is at least one selected from biphenyl type epoxy resin, o-cresol novolac type epoxy resin, phenol novolac type epoxy resin, salicylaldehyde novolac type epoxy resin and naphthol novolac type epoxy resin.
7. The composite powder according to any one of claims 1 to 3, which is used for a magnetic core.
8. The composite powder according to any one of claims 1 to 3, which is used for transfer molding.
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2017
- 2017-11-30 WO PCT/JP2017/043190 patent/WO2019106810A1/en active Application Filing
- 2017-11-30 JP JP2019556497A patent/JP7081611B2/en active Active
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| CN1839182A (en) * | 2003-10-03 | 2006-09-27 | 达泰豪化学工业株式会社 | Spherical coated magnesium oxide powder and method for production thereof, and resin composition comprising the powder |
| JP2010047740A (en) * | 2008-07-22 | 2010-03-04 | Hitachi Chem Co Ltd | Thermosetting resin composition, substrate for loading photosemiconductor element using the same, method for producing the substrate, and photosemiconductor device |
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| CN111406085A (en) | 2020-07-10 |
| WO2019106810A1 (en) | 2019-06-06 |
| JP7081611B2 (en) | 2022-06-07 |
| JPWO2019106810A1 (en) | 2020-11-26 |
| JP2022109291A (en) | 2022-07-27 |
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