WO2019106813A1 - コンパウンド及びタブレット - Google Patents
コンパウンド及びタブレット Download PDFInfo
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- WO2019106813A1 WO2019106813A1 PCT/JP2017/043194 JP2017043194W WO2019106813A1 WO 2019106813 A1 WO2019106813 A1 WO 2019106813A1 JP 2017043194 W JP2017043194 W JP 2017043194W WO 2019106813 A1 WO2019106813 A1 WO 2019106813A1
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- compound
- resin
- epoxy resin
- metal element
- wax
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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
- C08G59/686—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 containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- 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
- C08G59/40—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 curing agents used
- C08G59/62—Alcohols or phenols
- C08G59/621—Phenols
-
- 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
-
- 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
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
- C08G8/08—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ
- C08G8/10—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ with phenol
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof
- C08L91/06—Waxes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
- H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
- H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
- H01F1/12—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials
- H01F1/14—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials metals or alloys
- H01F1/147—Alloys characterised by their composition
- H01F1/153—Amorphous metallic alloys, e.g. glassy metals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
- C08K2003/0856—Iron
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Definitions
- the present invention relates to compounds and tablets.
- a compound containing a metal powder and a resin composition is used as a raw material of various industrial products such as an inductor, an electromagnetic wave shield, or a bonded magnet according to various physical properties of the metal powder (see Patent Documents 1 and 2 below) ).
- Inductors are difficult to pass high frequency components, and so are used for noise removal and smoothing in filters and power supply circuits.
- the structural classification of the inductor includes a wire-wound type, a laminated type, a thin-film type, etc., and in large current applications such as a DC-DC converter, a wound-type inductor is often used.
- miniaturization of the inductor is also required.
- the miniaturization reduces the volume of the core of the inductor (core made of a magnetic material).
- the characteristic inductance at the time of direct current load
- Patent Document 3 discloses a technology related to a mold coil having a structure in which the coil is sealed with a magnetic mold resin (a resin in which a magnetic powder is dispersed in a resin), and excellent DC bias characteristics can be obtained. (Paragraph [0011] of the same document).
- Patent Document 4 discloses an inductor that does not cause occurrence of sealing unevenness using soft magnetic alloy powder.
- JP 2004-31786 A Unexamined-Japanese-Patent No. 8-273916 JP, 2009-260116, A JP, 2014-013803, A
- the present invention is a compound which is excellent in fluidity, excellent in mold releasability, capable of reducing molding burrs, and further capable of enhancing the mechanical strength of molded articles, and this compound It aims at providing a tablet obtained by using it.
- a compound according to one aspect of the present invention includes a resin composition containing an epoxy resin, a phenol resin, a wax, and an imidazole compound, and a metal element-containing powder, and the epoxy resin contains a crystalline epoxy resin,
- the wax contains montanic acid ester, and the content of the metal element-containing powder is 90% by mass or more based on the total mass of the compound.
- the crystalline epoxy resin may include at least one selected from the group consisting of biphenyl type epoxy resins and biphenyl aralkyl type epoxy resins.
- the metal element-containing powder may include Fe amorphous alloy powder.
- the imidazole compound may include an imidazole compound having an alkyl group having 8 or more carbon atoms.
- the compound according to one aspect of the present invention may be used in an inductor.
- the compound according to one aspect of the present invention may be used for transfer molding.
- a tablet according to another aspect of the present invention is formed using the compound according to the above aspect of the present invention.
- the tablet obtained by using can be provided.
- the compound according to the present embodiment includes a resin composition containing an epoxy resin, a phenol resin, a wax, and an imidazole compound, and a metal element-containing powder.
- the epoxy resin contains a crystalline epoxy resin
- the wax contains a montanic acid ester.
- the content of the metal element-containing powder in the compound according to the present embodiment is 90% by mass or more based on the total mass of the compound.
- the compound according to the present embodiment is excellent in flowability and releasability from the mold by having the above-mentioned configuration, and it is possible to reduce molding burrs and form a molded article excellent in mechanical strength. Can.
- the compound according to the present embodiment can be suitably used as a material (for example, a magnetic core) of an inductor.
- the application of the compound according to the present embodiment is not limited to the core of the inductor.
- various physical properties such as electromagnetic properties or thermal conductivity of the compound can be freely controlled, and the compound is used for various industrial products or their raw materials it can.
- Industrial products manufactured using the compound may be, for example, automobiles, medical devices, electronic devices, electric devices, information communication devices, home appliances, audio devices, and general industrial devices.
- the compound when the compound contains soft magnetic powder such as Fe—Si—Cr alloy or ferrite as metal element-containing powder, the compound may be used as a material (for example, a magnetic core) of the above-mentioned inductor (for example, EMI filter).
- the compound When the compound contains a permanent magnet as the metal element-containing powder, the compound may be used as a raw material of a bonded magnet.
- the compound When the compound contains iron and copper as metal element-containing powder, a formed body (for example, a sheet) formed of the compound may be used as an electromagnetic wave shield.
- the resin composition is a component that may include a resin, a curing agent, a curing accelerator, and an additive, and may be the remaining components (nonvolatile components) excluding the organic solvent and the metal element-containing powder.
- the additive is a component of the resin composition except the resin, the curing agent and the curing accelerator.
- the additive is, for example, a wax, a coupling agent or a flame retardant.
- the resin composition at least contains an epoxy resin as a resin, a phenol resin as a curing agent, an imidazole compound as a curing accelerator, and a wax.
- the epoxy resin comprises a crystalline epoxy resin
- the wax comprises a montanic acid ester.
- a resin composition has a function as a binder (binder) of metal element containing powder, and provides mechanical strength to the molded object formed from a compound. For example, when the compound is molded at high pressure using a mold, the resin composition is filled between the metal element-containing powders to bind the metal element-containing powders to one another. By curing the resin composition in the molded product, the cured product of the resin composition binds metal element-containing powders more firmly, and the mechanical strength of the molded product is improved.
- the resin composition contains a wax, by mixing the metal element-containing powder and the resin composition containing the wax, the wax and other components of the resin composition other than the wax are attached to the surface of the metal element-containing powder It can be formed.
- the wax and other components of the resin composition may cover the entire surface of the metal element-containing powder, or may partially cover the surface of the metal element-containing powder.
- the wax formed on the surface of the metal element-containing powder and the other components of the resin composition are filled between the metal element-containing powder when they are formed under high pressure in a mold, and bind the metal element-containing powder to one another. It can be done.
- the tablet becomes a cured product through the subsequent molding process including heating and pressing, and the resin composition functions as a strong binder.
- a tablet will be a hardening object which encloses the circumference of a coil of inductor parts after the above-mentioned forming process.
- the wax is attached to / formed on the surface of the metal element-containing powder by mixing with the metal element-containing powder and other components of the resin composition other than the wax.
- the wax and other components of the resin composition may cover the entire surface of the metal element-containing powder, or may partially cover the surface of the metal element-containing powder.
- the wax dissolves a part or all of the curing accelerator. This makes it possible to suppress the thermal aging of the compound and the tablet.
- the wax liquefies in the molding process including heating and pressurizing, imparts fluidity to the compound to improve the moldability, and separates from the metal element-containing powder and other components of the resin composition to obtain a mold.
- the curing accelerator dissolved in the wax accelerates the curing of the resin composition, and the wax is separated from the other components of the resin composition, and the binder other than the wax is a solid binder Acts as a
- the wax used in the present embodiment contains at least montanic acid ester (montan wax).
- Montan wax is more effective in improving the fluidity and releasability of the compound than other waxes, and is also excellent in the effect of reducing molding burrs and the effect of improving the mechanical strength of the molded body .
- the wax may include other waxes than montan wax.
- Other waxes include, for example, fatty acids such as stearic acid, 12-oxystearic acid and lauric acid; zinc stearate, calcium stearate, barium stearate, aluminum stearate, magnesium stearate, calcium laurate, zinc linoleate, Fatty acid salts such as calcium ricinoleate and zinc 2-ethylhexoate; stearic acid amide, oleic acid amide, erucic acid amide, behenic acid amide, palmitic acid amide, lauric acid amide, hydroxystearic acid amide, methylenebisstearic acid amide, ethylene Bisstearic acid amide, ethylene bis lauric acid amide, distearyl adipic acid amide, ethylene bis oleic acid amide, dioleyl adipic acid amide, N-stearyl stearic acid amide, -Fatty
- Examples of commercial products of montan wax include Licowax E, Licowax OP, Recolube E, Recolube WE40 (trade names, manufactured by Clariant Chemicals Co., Ltd.).
- Examples of commercially available products of polyethylene wax include Recolub H12, Licowax PE 520, Licowax PED 191 (trade names, manufactured by Clariant Chemicals Co., Ltd.).
- Examples of commercially available products of Amide wax include Recolive FA1 (trade name of Clariant Chemicals Co., Ltd., trade name) and DISPARLON 6650 (trade name of Kushimoto Kasei Co., Ltd.).
- the wax may be appropriately selected according to the requirements of the compound design, such as the fluidity of the compound, the releasability, the temperature and pressure at molding, and the melting point of the wax. From the viewpoint of further satisfying these requirements, the wax is particularly preferably Lico wax E (drop point 82 ° C., melt viscosity 30 mPa ⁇ s (100 ° C.)) among the above.
- the content of the wax in the compound according to this embodiment is preferably 0.3 to 1.2% by mass, more preferably 0.4 to 1.0% by mass, and still more preferably 0 based on the total mass of the compound. It may be from 0.5 to 0.9% by mass.
- the content of the wax is 0.3% by mass or more, the effect of improving the fluidity and the releasability of the compound, the effect of reducing the molding burr, and the effect of improving the mechanical strength of the molded body are higher. It is easy to get When the content of the wax is 1.2% by mass or less, it is easy to suppress the decrease in the moldability of the compound and the mechanical strength of the molded body due to the excessive amount of the wax.
- the total mass of the compound means the total mass of components (nonvolatile components) excluding volatile components such as organic solvents.
- the epoxy resin used in the present embodiment may be, for example, a resin having two or more epoxy groups in one molecule, but includes at least a crystalline epoxy resin.
- the crystalline epoxy resin has a relatively high melting point and is excellent in fluidity despite the relatively low molecular weight.
- the epoxy resin may contain another epoxy resin (noncrystalline epoxy resin) other than the crystalline epoxy resin.
- the epoxy resin examples include biphenyl type epoxy resin, biphenyl aralkyl type epoxy resin, stilbene type epoxy resin, diphenylmethane type epoxy resin, sulfur atom containing type epoxy resin, novolac type epoxy resin, dicyclopentadiene type epoxy resin, salicylaldehyde Type epoxy resin, copolymerized epoxy resin of naphthols and phenols, epoxy compound of aralkyl type phenol resin, bisphenol type epoxy resin, glycidyl ether type epoxy resin of alcohols, glycidyl ether of paraxylylene and / or metaxylylene modified phenolic resin Type epoxy resin, glycidyl ether type epoxy resin of terpene modified phenol resin, cyclopentadiene type epoxy resin, polycyclic aromatic ring modified phenol resin Ricidyl ether type epoxy resin, glycidyl ether type epoxy resin of naphthalene ring-containing phenol resin, glycidyl ester type
- crystalline epoxy resins examples include hydroquinone type epoxy resins, bisphenol type epoxy resins, thioether type epoxy resins, biphenyl type epoxy resins, biphenyl aralkyl type epoxy resins and the like.
- a crystalline epoxy resin which can be obtained, for example, GK-4292 (melting point: 120 ° C., melt viscosity: 0.14 Pa ⁇ s (150 ° C.)), GK-5079 (melting point: 78 ° C., melt viscosity: 0.08 Pa) ⁇ S (150 ° C.), GK-4299 (melting point: 90 ° C., melt viscosity: 0.19 Pa ⁇ s (150 ° C.)), GK-8001 (melting point: 115 ° C., melt viscosity: 0.18 Pa ⁇ s (150) C)), GK-4137 (melting point: 80 ° C., melt viscosity: 0.06 Pa ⁇ s (150 ° C.)), YDC-1312 (melting point: 138-145 ° C., melt viscosity: 0.01 Pa ⁇ s (150 ° C.) ), YSLV-80XY (melting point: 75 to 85 °
- biphenyl type epoxy resins and biphenyl aralkyl type epoxy resins are preferable because they can further improve the fluidity of the compound and the mechanical strength of the formed product, and NC3000-H and YX-4000H are commercially available products. It is suitable.
- the content of the epoxy resin in the compound according to the present embodiment is preferably 1.5 to 3.5% by mass, more preferably 2.0 to 3.5% by mass, and still more preferably, based on the total mass of the compound. It may be 2.5 to 3.0% by mass.
- the content of the epoxy resin is 1.5% by mass or more, the flowability of the compound and the mechanical strength of the molded article are more easily improved.
- the content of the epoxy resin is 3.5% by mass or less, the magnetic properties of the molded article tend to be favorable. However, even when the content of the epoxy resin is out of the above range, the effect according to the present invention can be obtained.
- Phenolic resins function as curing agents for epoxy resins.
- the phenol resin is not particularly limited, but in general, an epoxy resin cured with a low-temperature to room temperature curing type phenolic resin tends to have a low glass transition point and become a soft cured product. As a result, the molded body formed from the compound also tends to be soft. Therefore, as a phenol resin, it is preferable to use a heat curing type phenol resin which cures an epoxy resin with heating, and it is more preferable to use a phenol novolac resin. By using a phenol novolac resin, a cured product of an epoxy resin having a high glass transition temperature can be easily obtained, so that a molded article (such as an inductor) excellent in heat resistance and mechanical strength can be manufactured.
- the phenolic resin is, for example, an aralkyl type phenolic resin, a dicyclopentadiene type phenolic resin, a salicylaldehyde type phenolic resin, a novolak type phenolic resin, a copolymer type phenolic resin of benzaldehyde type phenol and an aralkyl type phenol, paraxylylene and / or metaxylylene modified From the group consisting of phenolic resin, melamine modified phenolic resin, terpene modified phenolic resin, dicyclopentadiene type naphthol resin, cyclopentadiene modified phenolic resin, polycyclic aromatic ring modified phenolic resin, biphenyl type phenolic resin, and triphenylmethane type phenolic resin It may be at least one selected.
- the phenolic resin may be a copolymer composed of two or more of the above.
- a commercial product of the phenol resin for example, Tamanor 758, 759 manufactured by Arakawa Chemical Industries, Ltd., or HP-850N manufactured by Hitachi Chemical Co., Ltd. may be used. One of these may be used alone, or two or more of these may be used in combination.
- the phenol novolac resin may be, for example, a resin obtained by condensation or cocondensation of 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, resorcin, 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 ⁇ -naphthol, ⁇ -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.
- the phenol resin 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 resorcin, catechol, bisphenol A, bisphenol F, and substituted or unsubstituted biphenol.
- the ratio of the active group (phenolic OH group) in the phenol resin which reacts with the epoxy group in the epoxy resin is preferably 0.5 to 1. relative to 1 equivalent of the epoxy group in the epoxy resin. There may be 5 equivalents, more preferably 0.8 to 1.2 equivalents, still more preferably 0.9 to 1.1 equivalents.
- the ratio of active groups in the phenolic resin is less than 0.5 equivalent, the curing rate of the resin composition (epoxy resin) tends to decrease. If the proportion of active groups in the phenolic resin is less than 0.5 equivalent, the glass transition temperature of the resulting cured product may be low, or the elastic modulus of the cured product may not be obtained.
- the resin composition may contain other curing agents other than phenolic resin.
- Other curing agents include, for example, curing agents that cure epoxy resins in the range of low temperature to room temperature such as aliphatic polyamines, polyaminoamides, and polymercaptans, and aromatic polyamines, acid anhydrides, and dicyandiamide (DICY) And the like. One of these may be used alone, or two or more of these may be used in combination.
- the content of the phenolic resin in the compound according to the present embodiment is preferably 0.6 to 2.5% by mass, more preferably 0.8 to 2.2% by mass, and still more preferably, based on the total mass of the compound. It may be 1.0 to 2.0% by mass.
- the content of the phenolic resin is 0.6% by mass or more, the mechanical strength of the molded article is easily improved.
- the content of the phenolic resin is 2.5% by mass or less, the magnetic properties of the molded article are likely to be good.
- the effect according to the present invention can be obtained even if the content of the phenol resin is out of the above range.
- the curing accelerator is, for example, a component that reacts with the epoxy resin to accelerate the curing of the epoxy resin.
- the curing accelerator used in the present embodiment includes an imidazole compound (imidazole curing accelerator).
- imidazole curing accelerator As an imidazole compound, an alkyl group substituted imidazole, and a benzimidazole etc. are mentioned, for example.
- imidazole compound By using an imidazole compound, a compound having good flowability and releasability can be obtained.
- the said compound and the tablet using it can show long-term storage stability also in a high temperature and high humidity environment. Furthermore, when the above compound or tablet is used as a material of the inductor, the resulting inductor exhibits excellent mechanical properties.
- the imidazole compound is preferably an imidazole compound having an alkyl group having 8 or more carbon atoms, and more preferably an imidazole compound having an alkyl group having 10 or more carbon atoms.
- an imidazole compound having an alkyl group having a carbon number of 8 or more a compound having better fluidity can be easily obtained, and the mechanical strength of the resulting molded article tends to be further improved.
- Examples of commercially available imidazole compounds include 2MZ-H, C11Z, C17Z, 1,2DMZ, 2E4MZ, 2PZ-PW, 2P4MZ, 1B2MZ, 1B2PZ, 2MZ-CN, C11Z-CN, 2E4MZ-CN and 2PZ-CN. , C11Z-CNS, 2P4MHZ, TPZ, SFZ (all manufactured by Shikoku Kasei Kogyo Co., Ltd., trade names), and the like. One of these may be used alone, or two or more of these may be used in combination.
- the resin composition may contain other curing accelerators other than the imidazole compound.
- the other curing accelerator is not particularly limited as long as it is a component that reacts with the epoxy resin to accelerate curing of the epoxy resin, and may be a known curing accelerator.
- the compounding quantity of the hardening accelerator in the compound which concerns on this embodiment should just be an quantity which the hardening acceleration effect is acquired, and is not specifically limited.
- the blending amount of the curing accelerator is preferably 0.1 to 30 parts by mass, more preferably 1 with respect to 100 parts by mass of the epoxy resin. It may be up to 15 parts by mass. It is preferable that content of a hardening accelerator is 0.001 mass part or more and 5 mass parts or less with respect to a total of 100 mass parts of the mass of an epoxy resin and a phenol resin.
- the content of the curing accelerator relative to the total mass of the epoxy resin and the phenol resin is less than 0.001 parts by mass, it is difficult to obtain a sufficient curing acceleration effect.
- the content of the curing accelerator exceeds 5 parts by mass, the storage stability of the compound tends to be reduced.
- the compounding amount and content of the curing accelerator are out of the above range, the effects according to the present invention can be obtained.
- the content of the imidazole compound in the compound according to the present embodiment is preferably 0.1 to 3.0 parts by mass, more preferably 0.6 to 3.0 parts by mass, further preferably 100 parts by mass of the epoxy resin. It may preferably be 0.7 to 2.5 parts by mass, particularly preferably 0.8 to 2.0 parts by mass.
- the content of the imidazole compound is 0.1 parts by mass or more, a sufficient curing promoting effect is easily obtained, and the mechanical strength of the molded body is easily improved.
- the content of the imidazole compound is 3.0 parts by mass or less, the storage stability of the compound is more easily improved. However, even when the content of the imidazole compound is out of the above range, the effects according to the present invention can be obtained.
- the coupling agent can improve the adhesion between the resin composition and the metal element-containing powder, and can improve the flexibility and mechanical strength of a molded article (such as an inductor) formed from a compound.
- the coupling agent may be, for example, at least one selected from the group consisting of silane compounds (silane coupling agents), titanium compounds, aluminum compounds (aluminum chelates), and aluminum / zirconium compounds.
- the silane coupling agent may be, for example, at least one selected from the group consisting of epoxysilane, mercaptosilane, aminosilane, alkylsilane, ureidosilane, acid anhydride silane and vinylsilane.
- epoxy based silane coupling agents and acid anhydride based silane coupling agents are preferred.
- the compound may include one of the above coupling agents, and may include more than one of the above coupling agents.
- the content of the coupling agent in the compound according to the present embodiment is preferably 0.1 to 0.7% by mass, more preferably 0.2 to 0.6% by mass, and more preferably, based on the total mass of the compound. May be 0.3 to 0.5% by mass.
- the content of the coupling agent is 0.1% by mass or more, the flexibility and the mechanical strength of the molded article are easily improved.
- the content of the coupling agent is 0.7% by mass or less, blocking of the compound does not easily occur.
- the effects according to the present invention can be obtained.
- the compounds may contain flame retardants because of their environmental safety, recyclability, moldability and low cost.
- the flame retardant is, for example, at least one selected from the group consisting of bromine flame retardants, stalk flame retardants, hydrated metal compound flame retardants, silicone flame retardants, nitrogen containing compounds, hindered amine compounds, organic metal compounds and aromatic engineering plastics It may be.
- the compound may include one of the above-described flame retardants, and may include more than one of the above-described flame retardants.
- the metal element-containing powder may contain, for example, at least one selected from the group consisting of elemental metals, alloys, and metal compounds.
- the metal element-containing powder may be made of, for example, at least one selected from the group consisting of simple metals, alloys, and metal compounds.
- the alloy may include at least one selected from the group consisting of solid solution, eutectic and intermetallic compounds.
- the alloy may be, for example, stainless steel (Fe-Cr alloy, Fe-Ni-Cr alloy, etc.).
- the metal compound may be, for example, 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 element-containing powder may be, for example, a base metal element, a noble metal element, a transition metal element, or a rare earth element.
- the metal element contained in the metal element-containing powder is, for example, 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 ( It may be at least one selected from the group consisting of Dy).
- the metal element-containing powder may contain an element other than the metal element.
- the metal element-containing powder may contain, for example, oxygen (O), beryllium (Be), phosphorus (P), boron (B), or silicon (Si).
- the metal element-containing powder may be magnetic powder.
- the metal element-containing powder may be a soft magnetic alloy or a ferromagnetic alloy.
- Metallic element-containing powders include, for example, Fe-Si alloys, Fe-Si-Al alloys (sendust), Fe-Ni alloys (permalloy), Fe-Cu-Ni alloys (permalloy), Fe-Co alloys (Permendur), Fe-Cr-Si alloy (electromagnetic stainless steel), Nd-Fe-B alloy (rare earth magnet), Sm-Fe-N alloy (rare earth magnet), Al-Ni-Co alloy
- the magnetic powder may be at least one selected from the group consisting of (alnico magnet) and ferrite.
- the ferrite may be, for example, spinel ferrite (such as Mn-Zn ferrite and Ni-Zn ferrite), hexagonal ferrite, or garnet ferrite.
- the metal element-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-element-containing powder may contain one of the above-described elements and compositions, and may contain two or more of the above-described elements and compositions.
- the metal element-containing powder may be Fe alone.
- the metal element-containing powder may be an iron-containing alloy (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 metal element-containing powder may be Fe amorphous alloy powder.
- the compound contains an Fe amorphous alloy powder as the metal element-containing powder, it is easy to produce a molded body which is further excellent in magnetic properties from the compound.
- Fe amorphous alloy powder Commercial products of Fe amorphous alloy powder include, for example, AW2-08, KUAMET-6B2 (all trade names of Epson Atomics Co., Ltd., DAP MS3, DAP MS7, DAP MSA10, DAP PB, DAP PC, DAP MKV49). , DAP 410L, DAP 430L, DAP HYB series (all trade names of Daido Steel Co., Ltd.), MH45D, MH28D, MH25D, and MH20D (all trade names of Kobe Steel, Ltd.) Or at least one of them may be used.
- AW2-08, KUAMET-6B2 all trade names of Epson Atomics Co., Ltd., DAP MS3, DAP MS7, DAP MSA10, DAP PB, DAP PC, DAP MKV49.
- DAP 410L, DAP 430L, DAP HYB series all trade names of Daido Steel Co., Ltd.
- MH45D MH28
- the particle diameter of the Fe amorphous alloy powder is not particularly limited as long as it does not hinder the shape of the inductor to be molded and the filling property to the coil, but at least one of the following conditions It is further preferable that Among the following conditions, Fe amorphous alloy powder is preferable as it satisfies more conditions.
- first peak and second peak Having at least two peaks (hereinafter referred to as first peak and second peak) in the particle size distribution as Fe amorphous alloy powder.
- first peak> second peak the magnitude relationship of the particle diameter
- second peak the particle diameter of the second peak
- the particle diameter of the second peak is 1/2 or less (preferably 1/3 or less) of the particle diameter of the first peak.
- the particle diameter of the second peak may be about 1/10 or more of the particle diameter of the first peak. This is because as the particle size decreases, the surface area of the particles increases, which in turn hinders the fluidity, and the limit is estimated to be about 1/10.
- ⁇ Third condition The intensity ratio of the second peak to the first peak (ratio of abundance ratio: intensity of second peak / intensity of first peak) is 0.2 or more and 0.6 or less (preferably 0.25) More than and 0.4 or less). The intensity ratio may be, for example, approximately 0.3.
- ⁇ Fourth condition> The particle diameter of the first peak is dispersed about 22 ⁇ m.
- ⁇ Fifth Condition> D90% of the particle size distribution is approximately 60 ⁇ m or less.
- the shape of the metal element-containing powder is not particularly limited.
- the individual metal element-containing powders may be, for example, spherical, flat or needle-like.
- the metal element-containing powder may contain a plurality of types of metal element-containing powders different in the contained element, and may contain a plurality of metal element-containing powders different in average particle diameter.
- the content of the metal element-containing powder in the compound according to the present embodiment is 90% by mass or more, preferably 92% by mass or more, and more preferably 94% by mass or more, based on the total mass of the compound. Good.
- the content of the metal element-containing powder is preferably 99.8% by mass or less, more preferably 98% by mass or less, and still more preferably 96% by mass or less, based on the total mass of the compound. Good.
- the content of the metal element-containing powder is 99.8% by mass or less, the flowability of the compound and the mechanical strength of the molded product are easily improved. However, even when the content of the metal element-containing powder exceeds the above upper limit value, the effects according to the present invention can be obtained.
- the content of the resin composition in the compound according to the present embodiment is preferably 0.2 to 10% by mass, more preferably 2 to 8% by mass, and still more preferably 4 based on the total mass of the compound. It is up to 6% by mass. With such contents, it is easy to achieve the moldability (flowability) of the compound and the tablet, the high strength of the obtained inductor and the inductor characteristics at a high level.
- any method can be applied as long as the resin composition can be adhered and formed on the surface of the metal element-containing powder.
- the resin composition adheres to the surface of the metal element-containing powder and coats the metal element-containing powder, whereby a compound can be obtained.
- the resin composition contains an epoxy resin, a phenol resin, and an imidazole compound as described above, and the resin is softened by heating and kneading these together with a wax to soften the resin, and the wax and resin composition are formed on the surface of the metal element-containing powder. Can be attached and formed.
- a kneading method using a kneader or a stirrer can be used.
- a metal element-containing powder, a resin such as an epoxy resin, a curing agent such as a phenol resin, a curing accelerator such as an imidazole compound, a wax, and a coupling agent may be kneaded in a tank. After the metal element-containing powder and the coupling agent are charged into the tank and mixed, the resin, the curing agent, the curing accelerator, and the wax may be charged into the tank to knead the raw materials in the tank.
- the curing accelerator may be put in the tank to further knead the raw material in the tank.
- a mixed powder of resin, curing agent, curing accelerator, and wax (resin mixed powder) is prepared in advance, and then metal element-containing powder and a coupling agent are kneaded to prepare metal mixed powder, and then The metal mixed powder and the resin mixed powder may be kneaded.
- the kneading time by the kneader is, for example, preferably 5 minutes or more, more preferably 10 minutes or more, and still more preferably 20 minutes or more, although it depends on the volume of the tank and the production amount of the compound.
- 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. If the kneading time is less than 5 minutes, kneading is insufficient, the formability of the compound is impaired, and the degree of curing of the compound tends to vary.
- the curing of the resin composition (for example, an epoxy resin and a phenol resin) proceeds in the tank, and the flowability and the formability of the compound tend to be impaired.
- heating temperature is based on the composition of a resin composition, it is not limited.
- the heating temperature is, for example, preferably 50 ° C. or more, more preferably 60 ° C. or more, and still more preferably 80 ° C. or more.
- the heating temperature is preferably 150 ° C. or less, more preferably 120 ° C. or less, and still more preferably 110 ° C. or less.
- the resin composition in the tank is softened to easily cover the surface of the metal element-containing powder, and the curing of the resin composition during kneading is easily suppressed.
- a tablet can be formed by filling a compound into a predetermined mold and molding it by pressure.
- the shape and size of the tablet are not particularly limited.
- the diameter of the tablet may be 5 mm or more, and the height (length) of the tablet may be 5 mm or more.
- the pressure for forming the tablet is, for example, preferably 500 MPa or more, more preferably 1000 MPa or more, and still more preferably 2000 MPa or more.
- the compound or tablet can form an inductor through processes such as transfer molding.
- the molding pressure is higher pressure molding, the strength becomes higher and the more suitable.
- molding is preferably performed at a molding pressure of 500 to 2,500 MPa, and in consideration of mass productivity and mold life, molding at a molding pressure of 1400 to 2000 MPa is more preferable.
- the density of the compact may be preferably 75% to 86%, more preferably 80% to 86%, based on the true density of the particles of the compound.
- the density of the compression molded body of the compound or the tablet is 75% or more and 86% or less with respect to the true density of the particles of the compound, an inductor having good magnetic properties and high mechanical strength can be manufactured.
- curing a resin composition is 150 degreeC or more, More preferably, it is 160 degreeC or more.
- the glass transition temperature of the resin cured product is 150 ° C. or higher, an excellent inductor with less reduction in strength even in a high temperature and severe environment is easily obtained.
- the glass transition temperature referred to in the present invention indicates the temperature at which tan ⁇ peaks in dynamic viscoelasticity measurement.
- the flexural strength at a temperature of 150 ° C. of the cured product obtained by curing the compound is preferably 40 MPa or more, more preferably 43 MPa, and still more preferably 45 MPa or more.
- the bending strength at a temperature of 150 ° C. of the cured product is 40 MPa or more, an inductor having high mechanical strength at high temperatures can be obtained.
- bending strength can be measured by the 3-point bending test of the molded object shape
- the compound according to the present embodiment has excellent storage stability.
- the storage stability referred to in the present invention means that the variation in bending strength and bending strength of an inductor (a compression-molded article after heat treatment) manufactured using a compound stored for a predetermined time is small. The more severe the environment to be stored, and the longer the storage time, the higher the storage stability. Assuming a practical environment, for example, if storage stability of about 5 days is shown in a high temperature and high humidity environment of 40 ° C./90%-RH, it is suitable for implementation, and storage stability of about 2 weeks is If it shows, it will be a level which does not have a problem in mass production of an actual product.
- Example 1 [Preparation of compound and tablet] 517 g of KUAMET 6B2 (product name made by Epson Atomics Co., Ltd.) as an Fe amorphous alloy, 423 g of SQ-I (product name made by BASF Corporation) as a carbonyl iron powder, KBM-403 (3-gly as a silane coupling agent Cidoxypropyltrimethoxysilane, 4.75 g, manufactured by Shin-Etsu Chemical Co., Ltd., was placed in a tank of a biaxial pressure kneader, and kneaded at room temperature (about 25 ° C.) for 20 minutes.
- KUAMET 6B2 product name made by Epson Atomics Co., Ltd.
- SQ-I product name made by BASF Corporation
- KBM-403 3-gly as a silane coupling agent Cidoxypropyltrimethoxysilane, 4.75 g, manufactured by Shin-Etsu Chemical Co., Ltd.
- NC 3000-H (biphenyl aralkyl type epoxy resin, manufactured by Nippon Kayaku Co., Ltd., trade name, epoxy equivalent 290, softening point 70 ° C., melt viscosity 0.03 Pa ⁇ s (150 ° C.)) 34.
- the resulting compound mass was allowed to cool naturally and crushed into compound powder.
- the compound powder was placed in a molding die having a diameter of 13 mm and a height of 13 mm and pressurized at 2000 MPa to obtain a cylindrical tablet.
- Example 2 Compounds and tablets were prepared in the same manner as in Example 1 except that the combinations and amounts of the epoxy resin, phenol resin, curing accelerator, wax, silane coupling agent, and metal element-containing powder shown in Table 1 were changed. did.
- the epoxy resin used in Examples 2 and 4 is a crystalline epoxy resin YX-4000H (biphenyl type epoxy resin, manufactured by Mitsubishi Chemical Corporation, trade name, epoxy equivalent 192, softening point 105 ° C., melt viscosity 0.003 Pa S (150 ° C.)).
- AW2-08 (trade name, manufactured by Epson Atomics Co., Ltd.) was additionally used as the Fe amorphous alloy.
- Comparative Examples 1 to 3 Compounds and tablets were prepared in the same manner as in Example 1 except that the combinations and amounts of the epoxy resin, phenol resin, curing accelerator, wax, silane coupling agent, and metal element-containing powder shown in Table 1 were changed. did.
- the epoxy resin used in Comparative Example 1 is a non-crystalline epoxy resin EXA 4750 (naphthalene type epoxy resin, manufactured by DIC Corporation, trade name, epoxy equivalent 162, softening point 86 ° C., melt viscosity 0.045 Pa ⁇ s ( 150 ° C.)).
- the curing accelerator used in Comparative Example 2 is PX-4PB (tetra (n-butyl) phosphonium tetraphenylborate, manufactured by Nippon Chemical Industrial Co., Ltd., trade name).
- the wax used in Comparative Example 3 is carnauba wax (manufactured by Toa Kasei Co., Ltd., trade name: carnauba wax fine powder type).
- the compound according to the present invention and the tablet produced using the same are excellent in transfer moldability, less in molding burrs and excellent in releasability.
- the compound according to the present invention and the inductor obtained using the tablet manufactured using the same are high in strength and excellent in durability.
- the compound and tablet which concern on this invention can be utilized as a raw material of not only an inductor but various industrial products, such as an electromagnetic wave shield and a bond magnet.
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Abstract
Description
樹脂組成物は、樹脂、硬化剤、硬化促進剤及び添加剤を包含し得る成分であって、有機溶媒と金属元素含有粉とを除く残りの成分(不揮発性成分)であってよい。添加剤とは、樹脂組成物のうち、樹脂、硬化剤及び硬化促進剤を除く残部の成分である。添加剤とは、例えば、ワックス、カップリング剤又は難燃剤等である。本実施形態に係るコンパウンドにおいて、樹脂組成物は、樹脂としてのエポキシ樹脂、硬化剤としてのフェノール樹脂、硬化促進剤としてのイミダゾール系化合物、及び、ワックスを少なくとも含有する。さらに、上記エポキシ樹脂は、結晶性エポキシ樹脂を含み、上記ワックスは、モンタン酸エステルを含む。
本実施形態では、ワックスは金属元素含有粉及びワックス以外の樹脂組成物の他の成分と共に混合することで、金属元素含有粉表面に付着・形成される。ワックス及び樹脂組成物の他の成分は金属元素含有粉の表面全体を被覆していてもよく、金属元素含有粉の表面を部分的に被覆していてもよい。また、ワックスは、硬化促進剤の一部又は全部を溶解していることが好ましい。これによりコンパウンド及びタブレットの熱的な経時劣化を抑制することが可能である。ワックスは、加熱・加圧を含む成形工程の際に液状化し、コンパウンドに流動性を付与して成形性を向上すると共に、金属元素含有粉及び樹脂組成物の他の成分から分離して金型との離型性を高める離型材の働きを有する。ワックスの液状化に伴い、ワックスに溶解していた硬化促進剤が樹脂組成物の硬化を促進し、ワックスは樹脂組成物の他の成分から分離して、ワックス以外の樹脂組成物が強固なバインダーとしての機能を果たす。
本実施形態で用いるエポキシ樹脂は、例えば、1分子中に2個以上のエポキシ基を有する樹脂であってよいが、少なくとも結晶性エポキシ樹脂を含む。結晶性のエポキシ樹脂は、分子量が比較的低いにもかかわらず、比較的高い融点を有し、かつ流動性に優れる。また、エポキシ樹脂は、結晶性エポキシ樹脂以外の他のエポキシ樹脂(非結晶性エポキシ樹脂)を含んでいてもよい。
フェノール樹脂は、エポキシ樹脂の硬化剤として機能する。フェノール樹脂としては特に制限はないが、一般的に、低温から室温硬化タイプのフェノール樹脂で硬化させたエポキシ樹脂は、ガラス転移点が低く軟らかい硬化物となる傾向にある。その結果、コンパウンドから形成された成形体も軟らかくなり易い。そのため、フェノール樹脂としては、加熱に伴ってエポキシ樹脂を硬化させる加熱硬化タイプのフェノール樹脂を用いることが好ましく、フェノールノボラック樹脂を用いることがより好ましい。フェノールノボラック樹脂を用いることで、ガラス転移点が高いエポキシ樹脂の硬化物が得られ易いため、耐熱性及び機械強度に優れた成形体(インダクタ等)を製造することができる。
硬化促進剤は、例えば、エポキシ樹脂と反応してエポキシ樹脂の硬化を促進させる成分である。本実施形態で用いる硬化促進剤は、イミダゾール系化合物(イミダゾール系硬化促進剤)を含む。イミダゾール系化合物としては、例えば、アルキル基置換イミダゾール、及び、ベンゾイミダゾール等が挙げられる。イミダゾール系化合物を用いることで、流動性及び離型性が良好なコンパウンドが得られる。また、上記コンパウンド及びそれを用いたタブレットは、高温・高湿な環境下においても長期保存安定性を示すことができる。さらに、上記コンパウンド又はタブレットをインダクタの材料として用いた場合、得られるインダクタは、優れた機械的特性を示す。
カップリング剤は、樹脂組成物と金属元素含有粉との密着性を向上させ、コンパウンドから形成される成形体(インダクタ等)の可撓性及び機械的強度を向上させることができる。カップリング剤は、例えば、シラン系化合物(シランカップリング剤)、チタン系化合物、アルミニウム化合物(アルミニウムキレート類)、及びアルミニウム/ジルコニウム系化合物からなる群より選ばれる少なくとも一種であってよい。シランカップリング剤は、例えば、エポキシシラン、メルカプトシラン、アミノシラン、アルキルシラン、ウレイドシラン、酸無水物系シラン及びビニルシランからなる群より選ばれる少なくとも一種であってよい。特に、エポキシ系のシランカップリング剤及び酸無水物系のシランカップリング剤が好ましい。コンパウンドは、上記のうち一種のカップリング剤を備えてよく、上記のうち複数種のカップリング剤を備えてもよい。
金属元素含有粉は、例えば、金属単体、合金及び金属化合物からなる群より選ばれる少なくとも一種を含有してよい。金属元素含有粉は、例えば、金属単体、合金及び金属化合物からなる群より選ばれる少なくとも一種からなっていてよい。合金は、固溶体、共晶及び金属間化合物からなる群より選ばれる少なくとも一種を含んでよい。合金とは、例えば、ステンレス鋼(Fe-Cr系合金、Fe-Ni-Cr系合金等)であってよい。金属化合物とは、例えば、フェライト等の酸化物であってよい。金属元素含有粉は、一種の金属元素又は複数種の金属元素を含んでよい。金属元素含有粉に含まれる金属元素は、例えば、卑金属元素、貴金属元素、遷移金属元素、又は希土類元素であってよい。金属元素含有粉に含まれる金属元素は、例えば、鉄(Fe)、銅(Cu)、チタン(Ti)、マンガン(Mn)、コバルト(Co)、ニッケル(Ni)、亜鉛(Zn)、アルミニウム(Al)、スズ(Sn)、クロム(Cr)、バリウム(Ba)、ストロンチウム(Sr)、鉛(Pb)、銀(Ag)、プラセオジム(Pr)、ネオジム(Nd)、サマリウム(Sm)及びジスプロシウム(Dy)からなる群より選ばれる少なくとも一種であってよい。金属元素含有粉は、金属元素以外の元素を含んでもよい。金属元素含有粉は、例えば、酸素(О)、ベリリウム(Be)、リン(P)、ホウ素(B)、又はケイ素(Si)を含んでもよい。金属元素含有粉は、磁性粉であってよい。金属元素含有粉は、軟磁性合金、又は強磁性合金であってよい。金属元素含有粉は、例えば、Fe-Si系合金、Fe-Si-Al系合金(センダスト)、Fe-Ni系合金(パーマロイ)、Fe-Cu-Ni系合金(パーマロイ)、Fe-Co系合金(パーメンジュール)、Fe-Cr-Si系合金(電磁ステンレス鋼)、Nd-Fe-B系合金(希土類磁石)、Sm-Fe-N系合金(希土類磁石)、Al-Ni-Co系合金(アルニコ磁石)及びフェライトからなる群より選ばれる少なくとも一種からなる磁性粉であってよい。フェライトは、例えば、スピネルフェライト(Mn-Znフェライト及びNi-Znフェライト等)、六方晶フェライト、又はガーネットフェライトであってよい。金属元素含有粉は、Cu-Sn系合金、Cu-Sn-P系合金、Cu-Ni系合金、又はCu-Be系合金等の銅合金であってもよい。金属元素含有粉は、上記の元素及び組成物のうち一種を含んでよく、上記の元素及び組成物のうち複数種を含んでもよい。
<第2の条件>第2ピークの粒子径が第1ピークの粒子径の1/2以下(好ましくは1/3以下)であること。また、下限値としては、第2ピークの粒子径が第1ピークの粒子径の1/10程度以上であってよい。これは、粒子径が小さくなるにつれて粒子の表面積が増加し、かえって流動性を阻害してしまうからであり、その限界が1/10程度と推定されるからである。
<第3の条件>第2ピークと第1ピークの強度比(存在率の比:第2ピークの強度/第1ピークの強度)が0.2以上かつ0.6以下(好ましくは0.25以上かつ0.4以下)であること。強度比は、例えば、略0.3であってよい。
<第4の条件>第1ピークの粒子径がほぼ22μmを中心に分散していること。
<第5の条件>粒度分布のD90%がほぼ60μm以下であること。
コンパウンドを製造する工程は、金属元素含有粉表面に樹脂組成物を付着・形成させることができればいかなる手法も適用可能である。例えば、金属元素含有粉と樹脂組成物とを加熱しながら混合することで、樹脂組成物が金属元素含有粉の表面に付着して金属元素含有粉を被覆し、コンパウンドを得ることができる。樹脂組成物は、前述した通りエポキシ樹脂、フェノール樹脂、及びイミダゾール系化合物を含むが、これらをワックスと共に加熱しながら混練することで樹脂を軟化させ、金属元素含有粉の表面にワックス及び樹脂組成物の他の成分を付着・形成させることができる。ワックスを含む均質な樹脂組成物を金属元素含有粉の表面に形成させることで、成形性(流動性)、離型性に優れ、成形バリの発生が少ないコンパウンド、及びそれから得られるタブレットを得ることができる。
コンパウンドを所定の金型に充填して加圧により成形することで、タブレットを形成することができる。タブレットの形状及び寸法は、特に制限はない。例えば、タブレットが円柱状である場合、タブレットの直径は5mm以上であってよく、タブレットの高さ(長さ)は5mm以上であってよい。タブレットを作製する際の成形圧力は、例えば、500MPa以上であることが好ましく、1000MPa以上であることがより好ましく、2000MPa以上であるとさらに好ましい。
コンパウンド又はタブレットは、トランスファー成形等の工程を経てインダクタを形成することができる。成形圧力は、高圧成形であるほど、高強度となり好適となる。トランスファー成形の場合、500~2500MPaの成形圧で成形することが好ましく、量産性及び金型寿命も考慮した場合、1400~2000MPaの成形圧で成形することがより好ましい。圧縮成形体の密度は、コンパウンドの粒子の真密度に対して、好ましくは75%以上86%以下、より好ましくは80%以上86%以下であってよい。コンパウンド又はタブレットの圧縮成形体の密度がコンパウンドの粒子の真密度に対して75%以上86%以下であると、磁気特性が良好で、機械強度が高いインダクタを製造することができる。
樹脂組成物が硬化してなる樹脂硬化物のガラス転移温度は、150℃以上であることが好ましく、より好ましくは160℃以上である。樹脂硬化物のガラス転移温度が150℃以上であることで、高温で過酷な環境下においても強度の低下が少ない優れたインダクタが得られ易い。なお、本発明で言うガラス転移温度は、動的粘弾性測定において、tanδがピークになる温度のことを示す。
コンパウンドが硬化してなる硬化体の150℃の温度における曲げ強度は、好ましくは40MPa以上であり、より好ましくは43MPaであり、さらに好ましくは45MPa以上である。硬化体の150℃の温度における曲げ強度が40MPa以上であると、高温において機械強度の高いインダクタを得ることができる。なお、曲げ強度は、100mm×10mm×3mmの棒状に成型した成形体の3点曲げ試験によって測定することができる。
本実施形態に係るコンパウンドは、優れた保存安定性を有する。本発明で言う保存安定性とは、所定時間保管されたコンパウンドを用いて作製したインダクタ(熱処理後の圧縮成形体)の曲げ強度及び抗折強度の変動が、小さいこととを言う。保管される環境が苛酷であればあるほど、また保管時間が長くなればなるほど保存安定性が高いと言える。実施用上の環境を想定した場合、例えば、40℃/90%-RHの高温高湿環境で5日ほどの保存安定性が示せれば実施用上好適であり、2週間ほどの保存安定性が示せれば実際の製品の量産上問題ない水準となる。
[コンパウンド及びタブレットの作製]
Feアモルファス合金としてKUAMET6B2(エプソンアトミックス株式会社製、商品名)517gと、カルボニル鉄粉末としてSQ-I(BASF株式会社製、商品名)423gと、シランカップリング剤としてKBM-403(3-グリシドキシプロピルトリメトキシシラン、信越化学工業株式会社製、商品名)4.75gとを二軸加圧ニーダーの槽に入れ、室温(約25℃)で20分間混練した。
表1に示したエポキシ樹脂、フェノール樹脂、硬化促進剤、ワックス、シランカップリング剤、金属元素含有粉の組み合わせ及び配合量に変更したこと以外は実施例1と同様にして、コンパウンド及びタブレットを作製した。実施例2及び4で用いたエポキシ樹脂は、結晶性エポキシ樹脂であるYX-4000H(ビフェニル型エポキシ樹脂、三菱ケミカル株式会社製、商品名、エポキシ当量192、軟化点105℃、溶融粘度0.003Pa・s(150℃))である。また、実施例3及び4では、Feアモルファス合金としてAW2-08(エプソンアトミックス株式会社製、商品名)を追加で用いた。
表1に示したエポキシ樹脂、フェノール樹脂、硬化促進剤、ワックス、シランカップリング剤、金属元素含有粉の組み合わせ及び配合量に変更したこと以外は実施例1と同様にして、コンパウンド及びタブレットを作製した。比較例1で用いたエポキシ樹脂は、非結晶性のエポキシ樹脂であるEXA4750(ナフタレン型エポキシ樹脂、DIC株式会社製、商品名、エポキシ当量162、軟化点86℃、溶融粘度0.045Pa・s(150℃))である。比較例2で用いた硬化促進剤は、PX-4PB(テトラ(n-ブチル)ホスホニウムテトラフェニルボレート、日本化学工業株式会社製、商品名)である。比較例3で用いたワックスは、カルナバワックス(東亜化成株式会社製、商品名:カルナバワックス微粉末タイプ)である。
実施例及び比較例で得られたタブレットを用いてトランスファー成形した際の流動性を、スパイラルフローにより評価した。100gのタブレットをトランスファー試験機に仕込み、金型温度150℃、成形圧力5MPa、成形時間180秒の条件でトランスファー成形し、その際のスパイラルフロー量をmm単位で測定した。スパイラルフロー量とは、上記金型に形成された渦巻き曲線(アルキメデスのスパイラル)状の溝内において、液化したタブレットが流れる長さ(液化したタブレットの流動距離)である。加熱により液化したタブレットが流動し易いほど、スパイラルフロー量は大きい。つまり、流動性に優れたタブレット(コンパウンド)のスパイラルフロー量は大きい。トランスファー試験機としては、株式会社小平製作所製の100KNトランスファー成型機(PZ-10型)を用いた。結果を表2に示す。
スパイラルフローで得られた成形品をスパイラルフロー測定用金型から剥がした際の離型状態を目視にて確認し、離型性が良好であるものをA、離型性が悪いものをBと評価した。結果を表2に示す。
スパイラルフローで得られた成形品のバリの状態を目視で確認し、バリが最も大きい部分の染みだし幅をmm単位で測定した。結果を表2に示す。
実施例及び比較例で得られたコンパウンドを、油圧プレス機を用いて2000MPaの成形圧力にて長さ100mm×幅10mm×厚さ2mmの板形状の圧縮成形体に成形した。得られた板形状の圧縮成形体を窒素ガス(N2)雰囲気下、180℃の温度にて10分間加熱することで硬化させ、強度評価用の試験片(硬化体)を作製した。次に、試験片に厚み方向の加重を印加して、試験片が破断したときの加重の最大値から破断強度(MPa)を算出した。結果を表2に示す。
Claims (7)
- エポキシ樹脂、フェノール樹脂、ワックス、及びイミダゾール系化合物を含有する樹脂組成物と、金属元素含有粉と、を含み、
前記エポキシ樹脂が結晶性エポキシ樹脂を含み、
前記ワックスがモンタン酸エステルを含み、
前記金属元素含有粉の含有量がコンパウンドの全質量を基準として90質量%以上である、コンパウンド。 - 前記結晶性エポキシ樹脂が、ビフェニル型エポキシ樹脂及びビフェニルアラルキル型エポキシ樹脂からなる群より選ばれる少なくとも一種を含む、請求項1に記載のコンパウンド。
- 前記金属元素含有粉がFeアモルファス合金粉を含む、請求項1又は2に記載のコンパウンド。
- 前記イミダゾール系化合物が、炭素数8以上のアルキル基を有するイミダゾール系化合物を含む、請求項1~3のいずれか一項に記載のコンパウンド。
- インダクタに用いられる、請求項1~4のいずれか一項に記載のコンパウンド。
- トランスファー成形に用いられる、請求項1~5のいずれか一項に記載のコンパウンド。
- 請求項1~6のいずれか一項に記載のコンパウンドを用いて形成されたタブレット。
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| CN201780097274.9A CN111386295B (zh) | 2017-11-30 | 2017-11-30 | 复合物及料片 |
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| CN111640567B (zh) * | 2020-05-29 | 2022-02-11 | 深圳顺络电子股份有限公司 | 一种软磁合金材料的制备方法及软磁合金材料 |
| CN111640567A (zh) * | 2020-05-29 | 2020-09-08 | 深圳顺络电子股份有限公司 | 一种软磁合金材料的制备方法及软磁合金材料 |
| EP4137249A4 (en) * | 2020-07-14 | 2023-09-27 | Resonac Corporation | COMPOUND FOR BONDED MAGNETS, MOLDED BODY AND BONDED MAGNET |
| JP2022187217A (ja) * | 2021-06-07 | 2022-12-19 | 住友ベークライト株式会社 | 樹脂成形材料、成形体および当該成形体の製造方法 |
| JP2023075583A (ja) * | 2021-11-19 | 2023-05-31 | 住友ベークライト株式会社 | 樹脂成形材料、成形品および当該成形品の製造方法 |
| JP2023108807A (ja) * | 2022-01-26 | 2023-08-07 | 住友ベークライト株式会社 | 樹脂成形材料、成形品および当該成形品の製造方法 |
| JPWO2024143073A1 (ja) * | 2022-12-26 | 2024-07-04 | ||
| WO2024142176A1 (ja) * | 2022-12-26 | 2024-07-04 | 株式会社レゾナック | コンパウンド、タブレット、成形体、及び異方性ボンド磁石 |
| WO2024143073A1 (ja) * | 2022-12-26 | 2024-07-04 | 株式会社レゾナック | コンパウンド、タブレット、成形体、及び異方性ボンド磁石 |
| WO2024142174A1 (ja) * | 2022-12-26 | 2024-07-04 | 株式会社レゾナック | 磁性成形体の製造方法、及び異方性ボンド磁石の製造方法 |
| JP7298804B1 (ja) | 2022-12-26 | 2023-06-27 | 株式会社レゾナック | 磁性成形体の製造方法、及び異方性ボンド磁石の製造方法 |
| JPWO2025211171A1 (ja) * | 2024-04-01 | 2025-10-09 | ||
| WO2025211171A1 (ja) * | 2024-04-01 | 2025-10-09 | 住友ベークライト株式会社 | タブレット状のエポキシ樹脂成形材料、柱状タブレットおよび柱状タブレットの製造方法 |
| JP7845585B2 (ja) | 2024-04-01 | 2026-04-14 | 住友ベークライト株式会社 | タブレット状のエポキシ樹脂成形材料、柱状タブレットおよび柱状タブレットの製造方法 |
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| JP7081612B2 (ja) | 2022-06-07 |
| CN111386295B (zh) | 2024-01-09 |
| EP3719050B1 (en) | 2025-12-31 |
| EP3719050A1 (en) | 2020-10-07 |
| US11732124B2 (en) | 2023-08-22 |
| JP7416124B2 (ja) | 2024-01-17 |
| JP2022116173A (ja) | 2022-08-09 |
| CN117736548A (zh) | 2024-03-22 |
| EP3719050A4 (en) | 2020-11-18 |
| US20200385566A1 (en) | 2020-12-10 |
| JPWO2019106813A1 (ja) | 2021-01-21 |
| CN111386295A (zh) | 2020-07-07 |
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