Patent Application
20140077120
The present invention belongs to the technical field of magnetically enhanced resins and coating materials or the like using the same.
Resin-bonded magnetic materials are characterized by moldability at a low temperature, machine processability, precision moldability, low magnetic loss at high frequency, etc. In particular, due to the low magnetic loss at high frequency thereof, magnetic materials are expected to be applied to specially shaped small magnetic components etc. However, conventional resin-bonded magnetic materials have low magnetic permeability, which limits the use thereof as magnetic materials.
Meanwhile, it was known that addition of a thermosetting resin and a metal chelate compound to a Mn—Zn ferrite powder improves the magnetic properties of the resulting composition (see Non Patent Literature 1). However, the literature described only that an equal amount of a Co chelate powder, a Fe chelate powder, a Mn chelate powder, and a Ni chelate powder were blended, and did not reveal specific constitutions as to what kind of compound was used as a chelating agent, what kind of solvent was used, etc.
A major objective is to provide a magnetically enhanced resin and the like having an improved magnetic permeability.
The present inventors wholeheartedly conducted intensive investigations and found that a resin containing a ferromagnetic material, a compound having a macrocyclic π electronic structure, and an adhesive resin has an improved magnetic permeability.
The present invention includes the following.
According to the present invention, the magnetic permeability of a magnetically enhanced resin can be improved. In more detail, the use of the magnetically enhanced resin lowers magnetoresistance and thereby improves the magnetic efficiency of various devices utilizing magnetism (hereinafter magnetic application devices), such as a motor, a generator, a magnetic coil, a magnetic transformer, a magnetic noise filter, etc.
The magnetically enhanced resin of the present invention contains a ferromagnetic material, a compound having a macrocyclic π electronic structure, and an adhesive resin.
The magnetically enhanced resin of the present invention contains a ferromagnetic material. A ferromagnetic material is a material which, when placed in a magnetic field, is strongly magnetized in the direction of the applied field and shows residual magnetization even after the magnetic field is removed. The ferromagnetic material is not particularly limited, and examples thereof include soft magnetic materials, such as iron, silicon steel, permalloy, supermalloy, mu-metal, sendust, permendur, a soft ferrite, an amorphous magnetic alloy, and a nano crystal magnetic alloy; hard magnetic materials, such as an alnico magnet, a ferrite magnet, a samarium cobalt magnet, a neodymium iron boron magnet, and a samarium iron nitrogen magnet; and magnetostrictive materials, such as nickel and ferrite.
The examples of the ferromagnetic material also include a Fe—Ni alloy, a Fe—Co alloy, a Fe—Ni—Mo alloy, a Fe—Ni—Cu alloy, a Fe—Ni—Cr alloy, and a Fe—Al—Si alloy.
Here, permalloy is a ferromagnetic alloy which contains Fe and Ni as principal components. Permalloy also includes those containing, in addition to Fe and Ni, one or more kinds of Cr, Cu, and Mo. Supermalloy is a ferromagnetic alloy which contains Fe, Ni, and Mo as principal components and which is a kind of permalloy. Mu-metal is a ferromagnetic alloy which contains Fe, Ni, Cu, and Cr as principal components and which is a kind of permalloy. Sendust is a ferromagnetic alloy which contains Fe, Si, and Al as principal components.
Preferred ferromagnetic materials include soft magnetic materials, such as iron, silicon steel, permalloy, supermalloy, mu-metal, sendust, permendur, a soft ferrite, an amorphous magnetic alloy, and a nano crystal magnetic alloy, and more preferred are permalloy, supermalloy, sendust, and ferrite. Preferred ferromagnetic materials include a Fe—Ni alloy, a Fe—Co alloy, a Fe—Ni—Mo alloy, a Fe—Ni—Cu alloy, a Fe—Ni—Cr alloy, and a Fe—Al—Si alloy. The ferromagnetic material may be used alone or as a mixture of two or more thereof.
The ferromagnetic material is preferably a powder and more preferably a fine powder. The average particle size of the powder of the ferromagnetic material is preferably 0.1 to 100 μm, and more preferably 0.5 to 50 μm. The ferromagnetic material processed into a powder state can be uniformly distributed in the magnetically enhanced resin with ease. The magnetically enhanced resin in a powder state can be processed into a hardened body by calcinating at a low temperature.
The amount of the contained ferromagnetic material is preferably 50 to 95 parts by weight, and more preferably 75 to 95 parts by weight relative to 100 parts by weight of the solid components.
As used herein, the term “solid components” refers to a ferromagnetic material, a compound having a macrocyclic π electronic structure, and an adhesive resin.
Compound having Macrocyclic π Electronic Structure
The magnetically enhanced resin of the present invention contains a compound having a macrocyclic π electronic structure. The compound having a macrocyclic π electronic structure is a planar molecule which has one or more cyclic structures and in which the number of π electrons equals 4n+2 (wherein n is 0 or a positive integer). The compound having a macrocyclic π electronic structure is not particularly limited, and examples thereof include phthalocyanine, porphyrin, polycyanine, crown ether, cyclen, and cyclam. The compound having a macrocyclic π electronic structure may be used alone or as a mixture of two or more thereof.
The compound may include an ether bond, a carbonyl group, an ester bond, and a carbon-carbon double bond in the ring. The compound may be substituted with any substituent. Examples of the substituent in the compound include an alkyl group, an alkynyl group, an alkenyl group, an aryl group, an alkoxy group, an alkylenedioxy group, an aryloxy group, an aralkyl group, an aralkyloxy group, a heteroaryloxy group, an alkylthio group, a cycloalkyl group, an aliphatic heterocyclic group, an arylthio group, an aralkylthio group, a heteroarylthio group, an amino group, a substituted amino group, a cyano group, a hydroxyl group, a sulfo group, an oxo group, a nitro group, a mercapto group, and a halogen atom. These substituents may be further substituted with another substituent. The compound may be colorless or colored.
The compound preferably has two or more unshared electron pairs in the molecule. Such a compound having two or more unshared electron pairs in the molecule can serve as a chelating agent and form coordinate bonds with a metal atom.
The compound having a macrocyclic π electronic structure may be used alone. Alternatively, a coordination complex of the compound with a metal atom, a metal halide, a metal oxide, or the like may be used. Examples of the metal ion with which the compound forms a coordination complex include iron, cobalt, copper, silver, zinc, tin, manganese, nickel, sodium, magnesium, aluminium, lithium, zirconium, etc. Examples of the metal halide or the metal oxide with which the compound forms a coordination complex include SnCl2, SiCl4, AlCl3, FeCl3, TiO2, TiO, etc. The metal atom may be used alone or as a mixture of two or more thereof.
Examples of the compound having a macrocyclic π electronic structure include compounds, such as phthalocyanine, porphyrin, polycyanine, crown ether, cyclen, and cyclam;
coordination complexes of phthalocyanine with a metal atom etc., such as phthalocyanine cobalt(II), phthalocyanine copper(II) (α-form), phthalocyanine copper(II) (β-form), phthalocyanine iron(II), phthalocyanine magnesium(II), phthalocyanine chloro aluminum, phthalocyanine dilithium, phthalocyanine lead, phthalocyanine silicon dichloride, phthalocyanine silver, phthalocyanine tin(IV) dichloride, Pigment Blue 15, phthalocyanine sodium, phthalocyanine tin(II), and phthalocyanine zinc;
coordination complexes of a phthalocyanine compound or a substitution product thereof with a metal atom etc., such as 2,9,16,23-tetra-tert-butylphthalocyanine copper(II), and 1,2,3,4,8,9,10,11,15,16,17,18,22,23,24,25-hexadecafluorophthalocyanine copper(II);
substitution products of porphyrin, such as
5-(4-carboxyphenyl)-10,15,20-triphenylporphyrin,
5,15-diphenylporphyrin,
5-(4-methoxycarbonylphenyl)-10,15,20-triphenylporphyrin,
2,3,7,8,12,13,17,18-octaethylporphyrin,
2,3,7,8,12,13,17,18-octafluoro-5,10,15,20-tetrakis(pentafluorophenyl)porphyrin, protoporphyrin disodium,
tetraphenylporphyrin, tetrakis(4-carboxyphenyl)porphyrin,
5,10,15,20-tetrakis(4-aminophenyl)porphyrin,
5,10,15,20-tetrakis(4-carboxymethyloxyphenyl)porphyrin,
5,10,15,20-tetrakis(2,6-dichlorophenyl)porphyrin,
5,10,15,20-tetrakis(3,5-dihydroxyphenyl)porphyrin,
5,10,15,20-tetrakis(3,5-dimethoxyphenyl)porphyrin,
5,10,15,20-tetrakis(4-hydroxyphenyl)porphyrin,
5,10,15,20-tetrakis(4-methoxypheny)porphyrin,
5,10,15,20-tetrakis(pentafluorophenyl)porphyrin,
5,10,15,20-tetrakis(2,4,6-trimethylphenyl)porphyrin,
meso-tetraphenylchlorin, tetraphenylporphine,
5,10,15,20-tetra(4-pyridyl)porphyrin,
α,β,γ,δ-tetrakis(1-methylpyridinium-4-yl)porphyrin-p-toluenesulfonate, and tetraphenylporphyrintetrasulfonic acid;
coordination complexes of porphyrin or a substitution product thereof with a metal atom etc., such as bis(zinc porphyrin), hemin,
oxo[5,10,15,20-tetra(4-pyridyl)porphyrinato]titanium(IV),
pentamethylenebis[4-(10,15,20-triphenylporphin-5-yl)benzoate]dizinc(II), and
[5,10,15,20-tetrakis(4-methoxypheny)porphyrinato]cobalt(II);
substitution products of polycyanine, crown ether, cyclen, cyclam, etc.; and
coordination complexes of a compound such as polycyanine, crown ether, cyclen, and cyclam or a substitution product thereof, with a metal atom etc. Preferred as the compound having a macrocyclic π electronic structure are compounds, such as phthalocyanine, porphyrin, polycyanine, crown ether, cyclen, and cyclam, and particularly preferred are phthalocyanine, porphyrin, and polycyanine.
The amount of the contained compound having a macrocyclic π electronic structure is preferably 0.01 to 20 parts by weight, and more preferably 0.01 to 5 parts by weight relative to 100 parts by weight of the solid components. Also, the amount of the contained compound having a macrocyclic π electronic structure is preferably 0.01 to 40 parts by weight, and more preferably 0.01 to 10 parts by weight relative to 100 parts by weight of the ferromagnetic material.
The magnetically enhanced resin of the present invention contains an adhesive resin. The adhesive resin is not particularly limited, and examples thereof include thermoplastic resins, such as a polyvinyl acetate resin, a polyvinyl acetal, an ethylene-vinyl acetate resin, a poly vinyl chloride resin, an acrylic resin, a polyamide, a cellulose, a polycarbonate resin, and an α-olefin; and thermosetting resins, such as a urea resin, a melamine resin, a phenol resin, a resorcinol resin, an epoxy resin, a structural acrylic resin, a polyester, a polyurethane, a silicone resin, a fluorosilicone resin, and a polyaromatic. In terms of coating properties, preferred among them are an epoxy resin, a melamine resin, a polyimide resin, a polycarbonate resin, a phenol resin, and a fluorosilicone resin, and more preferred are a resol-type phenol resin and a fluorosilicone resin. The amount of the contained adhesive resin is preferably 5 to 50 parts by weight, and more preferably 5 to 25 parts by weight relative to 100 parts by weight of the solid components. Due to the contained adhesive resin, the magnetically enhanced resin of the present invention can exert an adhesive force. Moreover, the adhesion resin serves as a binder and as a result the ferromagnetic material, the compound having a macrocyclic π electronic structure, and other optional components can be uniformly mixed.
The magnetically enhanced resin of the present invention may contain a solvent. The solvent is not particularly limited as long as the compound having a macrocyclic π electronic structure, the magnetic material, the adhesive resin, and other optional components can be dissolved therein.
Examples of organic solvents include, aliphatic hydrocarbons, such as pentane, hexane, heptane, octane, and cyclohexane; aromatic hydrocarbons, such as benzene, toluene, and xylene; halohydrocarbons, such as dichloromethane, 1,2-dichloroethane, chloroform, tetrachloromethane, and o-dichlorobenzene; alcohols, such as methanol, ethanol, isopropyl alcohol, t-butyl alcohol, and t-amylalcohol; glycols, such as ethylene glycol, propylene glycol, diethylene glycol, and butyl carbitol; ethers, such as dimethyl ether, ethylmethyl ether, diethyl ether, diisopropyl ether, diglyme, tert-butyl methyl ether, dimethoxyethane, ethylene glycol diethyl ether, tetrahydrofuran, and 1,4-dioxane; amides, such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone; sulfoxides, such as dimethyl sulfoxide; nitriles, such as acetonitrile, propionitrile, and benzonitrile; ketones, such as acetone, methylethyl ketone, and methylisobutyl ketone; ester compounds, such as methyl acetate and ethyl acetate; aprotic polar solvents, such as N,N-dimethylformamide (DMF), dimethylacetamide (DMA), dimethyl sulfoxide (DMSO), and N-methyl-2-pyrrolidone (NMP); and high-boiling aromatic naphtha (trade name: Solvesso 150).
Examples of inorganic solvents include acidic solvents, such as hydrochloric acid, sulfuric acid, nitric acid, carbonic acid, and phosphoric acid; basic solvents, such as sodium hydroxide, magnesium hydroxide, calcium hydroxide, potassium hydroxide, and sodium hydrogen carbonate; and neutral solvents, such as pure water and brine.
Among the above solvents, organic solvents are preferred for uniform mixing of each component, and more preferred are butyl carbitol and methylethyl ketone.
The amount of the contained solvent is preferably 50 parts by weight or less, and more preferably 30 parts by weight or less relative to 100 parts by weight of the solid components. The solvent is an optional component and may be used or not used. In the cases where a mixing device (such as an automatic mortar grinder, a planetary mixer, a bead mill, or a ball mill) is used, it is possible that no or only a very small amount of the solvent is used. The added solvent may be vaporized by heat etc. or remain contained in the magnetically enhanced resin. The magnetically enhanced resin may contain abundant solvent and be in a liquid form, or contain a small amount of solvent and be in a semisolid or solid form.
The magnetically enhanced resin of the present invention may contain any optional compound etc. to the extent that the addition of such an optional compound etc. does not impair the effects of the present invention. Examples of the optional compound etc. that may be contained include a metal powder, a hydrophilic or hydrophobic silica powder, a clay powder, an organic powder such as an acrylic powder, a thixotropic agent such as an amide wax, a dehydrating agent such as calcium oxide, a diluent, a plasticizer, a flame retarder, a functional oligomer, a hindered amine compound, a hindered phenol compound, an age resistor such as
3-(2,2,6,6-tetramethylpiperidin-4-yloxy)propyltriethoxysilane, an ultraviolet absorber such as a benzotriazol compound, a pigment, a titanate coupling agent, an aluminium coupling agent, a silane coupling agent such as
3-glycidoxypropyltrimethoxysilane, a water resistance improver such as a blocked polyisocyanate, a drying oil, etc.
Mixing into Magnetically Enhanced Resin
The magnetically enhanced resin of the present invention can be produced by blending, in addition to a ferromagnetic material, a compound having a macrocyclic π electronic structure, and an adhesive resin, optional components such as a solvent as needed. The blending of the components may be performed using a mixing device, such as an automatic mortar grinder, a planetary mixer, a bead mill, or a ball mill until uniformly dispersed.
The magnetically enhanced resin of the present invention has a high magnetic permeability. Since a space filled up with the magnetically enhanced resin has a low magnetoresistance, more magnetic flux penetrates. That is, the use of the magnetically enhanced resin can improve the magnetic efficiency of magnetic application devices.
The form of the magnetically enhanced resin may be any of a solid, liquid, powder, gel, etc.
The magnetically enhanced resin in the form of a solid or powder can be used as a coating material after dissolved in a solvent. The resin in the form of a liquid or gel can be used as a coating material as it is.
The coating material can be applied to a targeted part of a magnetic application device by various kinds of methods using, for example, a coating tool such as a broad brush, a spray, a roller, a trowel, a brush, a spatula, or a coating machine such as a roll coater, a flow coater, or a vacuum impregnator.
Examples of the targeted part to which the coating material is applied include a plane or curved surface of, for example, a glass plate, a metal plate, etc. or a particular plane surface of a magnetic application device such as an electric motor, etc.
The magnetically enhanced resin can be used as a filler. The filler can be packed into a target part, for example a space etc. of a magnetic application device by, for example, spraying using a nozzle, or injection using a syringe, a tube, or a filling machine.
Since the magnetic permeability of the magnetically enhanced resin is higher than that of the air or the vacuum, application of the resin to an objective part or packing of the resin into a space of the magnetically enhanced resin reduces the magnetoresistance of the part and thereby improves the magnetic efficiency of the magnetic application devices.
The magnetically enhanced resin of the present invention can be made into a hardened body by calcination performed after application to a desired part. The hardened body can be produced by the steps of [1] applying the magnetically enhanced resin uniformly to form a coating, [2] drying the magnetically enhanced resin, and [3] calcinating the dried magnetically enhanced resin. The step of drying for producing the hardened body can be performed by leaving the resin, for example, at 30 to 80° C. for 30 minutes. The step of calcination for producing the hardened body can be performed by calcination, for example, at 120 to 200° C. for 5 to 100 minutes.
Since the hardened body has a high magnetic permeability, the magnetoresistance is low and more magnetic flux penetrates. Providing the hardened body to part of a magnetic application device improves the magnetic efficiency of the magnetic application device.
A device having a magnetically enhanced layer consisting of the above magnetically enhanced resin or a hardened body thereof is called a magnetically enhanced body. Examples of the magnetically enhanced body include a motor, a magnetic coil, a magnetic transformer, a magnetic noise filter, a generator, etc. The magnetically enhanced body has a magnetically enhanced layer with a reduced magnetoresistance and thus the magnetic efficiency of the magnetic application device can be improved.
Hereinafter, the present invention will be illustrated in more detail by Examples, but it is not limited thereto.
As the adhesive resin, Resin A: a resol-type phenol resin (“AH-880” made by Lignyte Co., Ltd.) and Resin B: a fluorosilicone resin (“SIFEL2610” made by Shin-Etsu Chemical Co., Ltd.) were used.
As the ferromagnetic material, a sendust powder “SFR-FeSiAl” made by Nippon Atomized Metal Powders Corp. (average particle size: 15 μm) was used.
As the compound having a macrocyclic π electronic structure, phthalocyanine (hereinafter “Pc”) “P0355” made by Tokyo Chemical Industry Co., Ltd. was used.
For mixing of the raw materials, a planetary mixer “MAZERUSTAR-KK-2000” made by Kurabo Industries, Ltd. was used. For calcination of the coating material, an electrical oven “PH(H)-102” made by Tabai Espec Corp. was used.
Air core coil 1 was prepared by forming an enamel-covered copper wire into a prism form with a substantially rectangular cross-section and binding adjacent loops to each other with an adhesive. The air core cross-section area S1 is the cross-section area of the air core coil 1. The measured value of the air core cross-section area S1 was 60 mm2. The number of turns of the air core coil 1 was 75. The air core coil 1 was prepared in Toyama Industrial Technology Center. More number of turns of the air core coil results in more accurate measurement of inductance.
As the measuring instrument 2, an LF impedance analyzer “4196A” made by Yokogawa Hewlett-Packard, Ltd. was used. The measuring instrument 2 was connected with the air core coil 1. The measurement frequency was 100 kHz.
First, 8.0 parts by weight of Resin A, 91.9 parts by weight of the ferromagnetic material, and 0.1 part by weight of Pc were blended. To this, about 5 mL of butyl carbitol (made by Wako Pure Chemical Industries, Ltd.) and about 3 mL of methylethylketone (MEK) (made by Wako Pure Chemical Industries, Ltd.) were added and mixed using the planetary mixer to prepare a magnetically enhanced resin.
The thickness t0 of an optical microscope glass slide 3 (made by As One Corp.) was measured with a micrometer (made by Mitutoyo Corp., measurement range: 1 μm to 25 mm). The magnetically enhanced resin was applied onto the optical microscope glass slide 3 so that the coating thickness was about 100 μm. This was calcinated using the electrical oven at about 160° C. for about 30 minutes to form a magnetically enhanced resin layer 4. The optical microscope glass slide 3 and the magnetically enhanced resin layer 4 were collectively called test piece 5. The thickness t of the test piece 5 was measured with the micrometer. The thickness of the magnetically enhanced resin layer 4 was calculated as the difference between t and t0, and thereby the sample cross-section area S2 was determined. The sample cross-section area S2 means the cross-section area of the magnetically enhanced resin layer 4.
The measured value of the inductance L0 in a condition where nothing was inserted in the air core circuit 1 was 18.04 μH. Next, the test piece 5 was inserted into the air core circuit 1, and the inductance L was measured. Since the optical microscope glass slide 3 does not have any magnetic properties, the change in the inductance L resulting from the insertion of the test piece 5 is attributable to the magnetically enhanced resin layer 4. The magnetic permeability of the test piece 5 was calculated by Mathematical Expression 1. As a result, the relative permeability μ in Example 1 was 11.3.
μ=1+(L/L0−1)×(S2/S1) Mathematical Expression 1
The procedure was performed in the same manner as in Example 1 except that the blending ratios of the materials used were as shown in Table 1. The blending ratios and results are shown in Table 1. Each amount of the blended materials in Table 1 is expressed in parts by weight relative to 100 parts by weight of the solid components.
To prepare test pieces, the procedure was performed in the same manner as in Example 1 except that the blending ratios of the materials used were as shown in Table 2. The blending ratios and results are shown in Table 2.
To prepare test pieces, the procedure was performed in the same manner as in Example 1 except that Resin B was used as the adhesive resin and that the blending ratios of the materials used were as shown in Table 5. The blending ratios and results are shown in Table 3.
As is clear from Tables 1 to 3, blending Pc with the magnetically enhanced resin containing an adhesive resin and a ferromagnetic material improves the relative permeability of the adhesive resin.
The magnetically enhanced resin or the like of the present invention, of which the magnetic permeability is improved, is industrially useful.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2011-109846 | May 2011 | JP | national |
| Filing Document | Filing Date | Country | Kind | 371c Date |
|---|---|---|---|---|
| PCT/JP2012/053784 | 2/17/2012 | WO | 00 | 12/4/2013 |
