WO2002083982A1 - Tole magnetique presentant un revetement isolant, et revetement isolant - Google Patents
Tole magnetique presentant un revetement isolant, et revetement isolant Download PDFInfo
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- WO2002083982A1 WO2002083982A1 PCT/JP2002/003571 JP0203571W WO02083982A1 WO 2002083982 A1 WO2002083982 A1 WO 2002083982A1 JP 0203571 W JP0203571 W JP 0203571W WO 02083982 A1 WO02083982 A1 WO 02083982A1
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- resin
- steel sheet
- coating
- insulating coating
- fluororesin
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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
- H01F1/14766—Fe-Si based alloys
- H01F1/14775—Fe-Si based alloys in the form of sheets
- H01F1/14783—Fe-Si based alloys in the form of sheets with insulating coating
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
- B05D5/08—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain an anti-friction or anti-adhesive surface
- B05D5/083—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain an anti-friction or anti-adhesive surface involving the use of fluoropolymers
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/12—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of articles with special electromagnetic properties
- C21D8/1277—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of articles with special electromagnetic properties involving a particular surface treatment
- C21D8/1283—Application of a separating or insulating coating
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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
- H01F1/14766—Fe-Si based alloys
- H01F1/14791—Fe-Si-Al based alloys, e.g. Sendust
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S428/00—Stock material or miscellaneous articles
- Y10S428/90—Magnetic feature
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
- Y10T428/263—Coating layer not in excess of 5 mils thick or equivalent
- Y10T428/264—Up to 3 mils
- Y10T428/265—1 mil or less
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31511—Of epoxy ether
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y10T428/31533—Of polythioether
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- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/3154—Of fluorinated addition polymer from unsaturated monomers
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y10T428/31544—Addition polymer is perhalogenated
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- Y10T428/31678—Of metal
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
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- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31855—Of addition polymer from unsaturated monomers
- Y10T428/31935—Ester, halide or nitrile of addition polymer
Definitions
- the present invention relates to an electromagnetic steel sheet having an insulating coating.
- the electromagnetic steel sheet having the insulating coating is mainly used for producing a laminated iron core by being subjected to processing such as shearing and punching, but the present invention is not limited to such use.
- the present invention has an insulating coating that has extremely high punching properties, high slipperiness between steel sheets, high adhesion, does not adhere to water droplets and stains that cause ⁇ , and has high corrosion resistance. It is intended to obtain an electromagnetic steel sheet having the following.
- the present invention also relates to a chromium-free coating suitable for use as the outermost layer of the insulating coating of the above-mentioned electromagnetic steel sheet.
- Insulating coatings on electrical steel sheets used for motors and transformers require interlayer resistance, but in addition, various characteristics are required from the viewpoint of convenience during processing and storage. Since the uses of magnetic steel sheets are diverse, various insulating coatings are being developed according to the use.
- the insulating coating is (1) an inorganic coating that emphasizes weldability and heat resistance and resists strain relief annealing; (2) a resin-containing semi-organic coating that resists strain relief annealing with the aim of achieving both punchability and weldability; 3) It is roughly classified into three types of organic coatings that cannot be annealed for special purposes.
- Speaking of the punching property reducing the abrasion of the punching die, generally, there is a tendency that (3)>(2)> (1) in order of decreasing order.
- the performance of motors and transformers has increased, the performance of electrical steel sheets has also tended to increase.
- the electrical steel sheet with excellent magnetic properties has a higher content of Si and the like, there is a problem that the hardness of the steel sheet increases and the punching property decreases. In addition, even for electrical steel sheets with low hardness, better punching properties are required to reduce costs by reducing the number of times of die polishing.
- a material in which chromate is the main component (matrix) and a resin such as acrylic, epoxy, vinyl acetate or the like is added has relatively high material properties (insulation). It is mainly used because of its good properties, coating adhesion and corrosion resistance.
- a fluorine-based resin as a resin to be added to the chromate.
- Japanese Patent Publication No. 4-43715 discloses a method of forming an insulating film in which a fluororesin or a polyethylene resin is dispersed in cuprate and the fluororesin is concentrated on the surface by baking. Have been.
- the Japanese Patent Publication No. 7-355584 describes that a coating solution containing a chromate and a phenol resin, perfluoroalkyloxetyleneethanol, etc. is applied and then baked. A formation method is disclosed.
- JP-A-7-288834, JP-A-7-28663, JP-A-7-314153 also disclose a chromate inorganic coating. There is disclosed an electromagnetic steel sheet in which a fluorine-based resin is present in an outer layer or an inner layer of resin particles therein.
- the fluororesin was unstable, and a resin having uniform and sufficient adhesion could not be obtained.
- An object of the present invention is to provide an electromagnetic steel sheet with an insulating coating having improved punching properties, high slipperiness, excellent handling properties during processing, and uniform and good adhesion.
- the punchability is remarkably improved even when used for a low-hardness steel sheet or a high-hardness steel sheet.
- the outermost coating of the magnetic steel sheet is chromium-free, that is, contains no Cr (substantially less than 1.0% by weight), and contains a fluororesin in an amount of from 20 parts by mass to 90 parts by mass.
- This is an electrical steel sheet with an insulating coating that has excellent workability, slipperiness, and adhesion. Further, it is a coating suitable for the outermost layer of an insulating coating of an electrical steel sheet, and does not contain Cr and contains a fluorine resin in an amount of 20 to 90 parts by mass. It is an insulating coating.
- the coefficient of kinetic friction on the surface of the insulating film is preferably 0.3 or less.
- the fluororesin is made of polytetrafluoroethylene (PTFE), tetrafluoroethylene-perfluoronoroloquinolebutyrene ether copolymer (PFA) and tetrafluoroethylene-hexafluoropropylene.
- PTFE polytetrafluoroethylene
- PFA tetrafluoroethylene-perfluoronoroloquinolebutyrene ether copolymer
- FEP copolymers
- Figure 1 is a graph showing the results of evaluation of the punching properties and adhesion after punching out electrical steel sheets.
- an electromagnetic steel plate (electric iron plate) is used.
- the electromagnetic steel sheet known ones can be used, and any one of a unidirectional, a non-directional, and a bidirectional may be used.
- the grain-oriented electrical steel sheet may or may not have a forsterite coating and / or a phosphate coating on its surface.
- the outermost coating containing a fluororesin described below is preferably applied directly on these materials.
- a further different coating layer (preferably an insulating coating) is provided between the outermost coating and the above materials. It is not prohibited to provide.
- a coating layer for example, a phosphate-based coating and an oxalate-based coating are suitable, and these may or may not contain a resin.
- the chemical composition of the magnetic steel sheet of the present invention is not particularly limited. Orientation (1 direction, 2 direction) Examples of electrical steel sheets are S: 2 to 4% by mass, Mn: ⁇ 0.4% by mass, A1: ⁇ 0.1% by mass.
- one or more of the inhibitor elements may be used in a total of 0.5 mass. % (Mn and A 1 alone are as described above).
- % Mn and A 1 alone are as described above.
- S i ⁇ 4% by weight (preferably 0.0 5 wt% or more)
- M n ⁇ 1. 0 mass 0/0
- a 1 ⁇ 3.
- the magnetic steel sheet when S i is 2.5% by mass or more, the magnetic steel sheet has high hardness, and when it is less than 2.5% by mass, the magnetic steel sheet has low hardness.
- the thickness of the electromagnetic steel sheet of the present invention is not particularly limited. It is preferably about 0.05 to 1.0 mm, which is a normal thickness.
- the outermost layer of the magnetic steel sheet of the present invention needs to be formed with a chromium-free insulating film containing a fluororesin (hereinafter referred to as the outermost layer film).
- the fluorine resin include polytetrafluoroethylene resin (PTFE), tetrafluoroethylene-perfluoroalkylbutyl ether copolymer (pFA), and tetrafluoroethylene-hexafluoropropylene copolymer (FEP).
- Trifluorinated ethylene resin Trifluorinated ethylene resin, vinylidene fluoride resin, vinyl fluoride resin, ethylene tetrafluoride-ethylene copolymer, and copolymers of these resins and ethylene resin.
- PTFE polymethyl methacrylate
- PFA polymethyl methacrylate
- FEP fluoride-ethylene copolymer
- the above-mentioned forsterite coating or phosphate coating may be present, or only the coating containing the fluororesin may be present.
- These inner layers are also generally insulative, and constitute an insulating film integrally with the outermost layer.
- the forsterite film is formed by applying an annealing separator mainly composed of MgO to the surface and reacting with ground iron by finish annealing.
- the preferred composition is forsterite (Mg 2 Si0 4 ) mainly (50% by mass or more with respect to the entire layer), and the balance contains iron oxide and incidental impurities.
- a preferred composition of the phosphate-based coating is that a phosphate such as magnesium phosphate, aluminum phosphate, or calcium phosphate is used as a main component (preferably containing 50% by mass or more),
- the composition further contains additives such as chromic acid, chromic acid salts, silica, and boric acid as necessary.
- the form of the fluororesin before forming the film is not particularly limited, but may be in the form of a solution dissolved in an organic solvent (preferably a pyrrolidone type), a nonionic surfactant, or the like. It can be used in a dispersed (disparged) or emulsified (emulsion) state, fine powder form, molding powder form, etc. In consideration of dispersibility, it is preferable to use a solution, a disperse ion, or an emulsion.
- the present invention improves the slipperiness of the coating surface by utilizing the phenomenon in which the fluorine resin is concentrated on the surface in the stage from application of the insulating coating to baking. Therefore, the content of the fluororesin in the outermost layer coating is 20 to 90 parts by mass with respect to 100 parts by mass of the outermost layer insulating coating, that is, 20 to 90 parts by mass on average, that is, 20 to 90% by mass is required.
- the average value is adopted because the fluororesin is concentrated in the surface layer as described above. If the amount is less than 20 parts by mass, the effect of improving the punchability expected by the present invention cannot be obtained. If the amount exceeds 90 parts by mass, the adhesion to the coating film is reduced.
- the preferred content of the fluororesin is 30 to 80 parts by mass. This situation is evident in Fig. 1, which shows how punchability and film adhesion change with respect to the content of fluorine resin in grain-oriented electrical steel sheets.
- grain-oriented electrical steel sheets (3i: 3.3% by mass%, Mn: 0.07%, A1 ⁇ 0.001%, and Sb, Sn, etc., remaining on the product plate out of the inhibitors are 0.5% or less in total, and the remaining iron and impurities are used.
- Forsterite coating is used as the lowermost layer, and Then, a phosphate coating was formed thereon, and an insulating coating made of a fluororesin (PTFE) and an organic resin (PES) was formed thereon as the outermost layer.
- the component other than the resin is preferably an organic resin or an inorganic compound, and their content in the outermost layer coating is 10 to 80% by mass, preferably 20 to 70% by mass.
- Organic resins other than fluororesins include epoxy resin, acrylic resin, vinyl acetate resin, phenol resin, polyethersulfone resin (PES), polyphenylene sulfide resin (PPS), polysulfone resin, and polysulfone resin.
- PES polyethersulfone resin
- PPS polyphenylene sulfide resin
- polysulfone resin and polysulfone resin.
- PES polyether ketone resin
- PPS polysulfone resin
- thermoplastic resins are heat-resistant thermoplastic resins, and are baked at a high temperature to concentrate high-melting fluororesins such as PTFE, PFA, FEP on the surface layer.
- PTFE thermoplastic resin
- PFA polymethyl methacrylate
- FEP fluororesins
- the effect of improving the adhesion to the base is obtained, which is more preferable.
- Especially preferred is the combination of PTFE and PES or PTFE and PPS.
- the inorganic compound examples include phosphates such as magnesium phosphate, aluminum phosphate, and calcium phosphate, and inorganic oxides of Group 3 or 4 of the periodic table such as alumina and silica.
- examples include metal compounds of Group 3 of the periodic table, such as aluminum compounds.
- Preferred are phosphates, such as magnesium phosphate and aluminum phosphate. In addition, one or a mixture of two or more of these can also be used.
- the outermost layer coating is chromium-free, it does not contain any Cr or Cr compound. (However, since Cr is highly reactive, it may not exist alone after the film formation treatment. rare). Therefore, Cr compounds are excluded from the above inorganic compounds.
- the Cr compound has good compatibility with steel sheets and is often used as an insulating coating material for electrical steel sheets.
- the fluororesin cannot be stably dispersed, and the fluororesin aggregates and separates.
- the fluororesin To disperse the fluororesin, it is necessary to modify the fluororesin (introduce a hydrophilic group, ie, a hydroxyl group, ethylene oxide, carboxylic acid, or amine by a method such as copolymerization or graft polymerization) or Excessive emulsification / dispersion is necessary, and as a result, the function of the fluororesin is weakened, and the original performance is impaired. For this reason, the formed film is uneven and has poor adhesion, and the effect of improving the punching property and the slipperiness is insufficient. Therefore, the insulating film of the present invention must not contain Cr and Cr compounds.
- the thickness of the insulating coating containing the fluororesin of the present invention is not particularly limited. However, if the coating amount is too small, the coating tends to be non-uniform, and the base or ground iron is easily exposed. The effect may be insufficient. On the other hand, if the amount is too large, swelling may occur at the time of baking, and paintability may decrease.
- the preferred average thickness of the outermost insulating film containing a fluororesin is
- the average thickness of the inner layer is preferably about 0.1 to 20 m.
- the average thickness was obtained by taking an enlarged photograph of the coating cross section obtained by embedded polishing or freeze fracture, measuring the thickness of the target coating at 10 points, and taking the arithmetic average.
- the weight loss per unit area (weight per unit area) when the target film was peeled off with a solvent or alkali was measured and correlated with the average thickness.
- the weight per unit area was calculated using the correlation line (calibration curve).
- the average thickness may be converted from the amount.
- the coating of the present invention may be applied to both surfaces, or may be applied to only one surface to produce the effect.
- the dynamic friction coefficient of the insulating coating containing the fluororesin of the present invention is preferably 0.3 or less, more preferably 0. 25 or less, more preferably 0.2 or less.
- the fluororesin be concentrated on the surface by heat treatment.
- the baking temperature is preferably equal to or higher than the melting point of the fluororesin (for example, 327 ° C for PTFE) or the glass dislocation point.
- the upper limit of the baking temperature is desirably set so that the fluorocarbon resin and matrix (organic resin or inorganic compound other than fluorocarbon resin) do not decompose.
- the baking temperature is above the melting point of the matrix (eg, 277 ° C for PPS) or glass transition temperature (eg, 225 ° C for PES). That is, for example, in the case of a composition containing PTFE and one or two of PES and PPS, the baking conditions are preferably about 330 to 480 and about 10 seconds to 2 hours.
- the upper limit of the baking temperature of 480 was set to a value near the lowest decomposition temperature (directly below) of the resin constituting the film.
- more preferable baking conditions are about 350 to 470 ° C and about 20 seconds to 1 hour. If the composition is within a suitable range, a value of about 0.1 in dynamic friction coefficient should be obtained. Can be done. Next, a film forming method for obtaining the electromagnetic steel sheet of the present invention will be described.
- the primer is preferably composed mainly of components other than the fluororesin in the outermost coating film.
- PES is preferably used.
- PPS is preferably used.
- a coating containing the above-mentioned chemicals, that is, a fluororesin and, if necessary, an organic resin and / or an inorganic compound is applied to an electromagnetic steel sheet, and baked to form a film.
- the ratio of the fluororesin and other solid components in the formed film is almost the same as the ratio of the solid components in the paint.
- the form of the paint is not particularly limited, and may be any of a solvent type, an aqueous solution type, a discharge purge type, a marsion type, and a slurry type.
- an insulating film containing the amount of the fluororesin within the range of the present invention can be formed.
- a rhono-coater method When forming the insulating coating, various methods commonly used in industrial applications such as a rhono-coater method, a flow coater method, a spray coating method, and a knife coater method can be applied.
- a rhono-coater method As for the baking method, hot air type, infrared type, induction heating type, radiant tube type, direct A fire type or the like can be applied.
- a preferred baking temperature is 150 to 500 ° C.
- additives such as a fire retardant and a pigment (added for coloring and for enhancing insulation) may be added to the paint.
- the total amount of the additives is preferably 300 parts by mass with respect to 100 parts by mass of the outermost insulating coating (excluding additives). It is effective to add the additive in an amount of at least 3 parts by weight.
- the inner layer coating when forming the inner layer coating, as in the case of the outermost layer, after applying the coating liquid by a usual industrial method, that is, a method such as a roll coater method, a flow coater method, a spray coating, or a knife coater method, It is preferable to bake by hot air, infrared, induction heating, radiant tube, or direct fire.
- the forsterite layer is usually formed by applying an annealing separator mainly composed of MgO to the surface before finish annealing and then performing finish annealing when manufacturing electrical steel sheets. It is a target.
- the electrical steel sheet of the present invention is an electrical steel sheet with an insulating coating having excellent punching properties and excellent slipperiness and excellent adhesion, it can be applied to any form of punching application. It can be preferably applied to stators, rotors, EI cores of transformers, and magnetic shielding materials.
- Si 3.3% by mass, ⁇ ⁇ 0.07% by mass, ⁇ 1: ⁇ 0.01% by mass, balance of Fe and impurities in one direction (direction )
- Electrical steel sheet Si: 3.0% by mass, Mn: 0.2% by weight, A1: 0.01% by weight, balance Fe and oriented magnetic steel sheet of impurities, Si: 3.0% by mass, Mn: 0.2% by mass, A1: 0.2% by mass, non-oriented electrical steel sheet with balance of Fe and impurities, and Si: 0.25% by mass, Mn : 0.25 mass%, A 1: 0.25% by mass, non-oriented electrical steel sheet with the balance Fe and impurities applied to the coating containing the components shown in Table 1 to form a 2 ⁇ m-thick uppermost insulating coating did.
- the undercoat was a forsterite coating (lower layer, thickness 4 m) and a phosphate-based coating (upper layer, thickness 3 ⁇ ), or a coating of only forsterite (thickness 4 / zm ),
- a forsterite coating lower layer, thickness 4 m
- a phosphate-based coating upper layer, thickness 3 ⁇
- a coating of only forsterite thickness 4 / zm
- One coated with a phosphate-based coating thickness 1 / ⁇
- one coated with a chromate-based coating thickness 0.3 ⁇
- the steel plate used had an average roughness of R a ⁇ 0.5 ⁇ .
- the paint for coating the uppermost layer was a solvent type, and a pyrrolidone solvent was used as the solvent.
- the coating was performed with a roll coater, baked at a sheet temperature of 400 ° C., and allowed to cool, and then subjected to the following evaluations.
- Fuorusuterai TMG annealing separator (composition M g O: 9 5 mass 0/0, T i O 2 ⁇ ⁇ 5 wt%) was applied with Myzus Rally, after drying, subjected to finish annealing
- a phosphate water-based paint such as phosphoric acid Mg, chromic acid, silica, etc.
- a roll coater to the phosphate-based coating applied to the forsterite layer on grain-oriented electrical steel sheets. Baked in.
- a water-based paint such as phosphoric acid A 1, chromate and boric acid was applied by a roll coater and baked at 300 ° C.
- the amount of Cr contained in the uppermost layer coating of the present invention is not more than 0.0% by weight.
- the clearance was set to 5 to 8% of the plate thickness, and continuous punching was performed using punching oil.
- the number of punches until the Paris height reached 50 m was measured and evaluated.
- the burr height is measured at four locations per punched material to obtain the maximum value,
- the average value of the maximum paris height of each of the three blanks was adopted.
- the punching speed was 450 minutes.
- the dynamic friction coefficient was measured using a surface property measuring instrument (Peeling / Slipping / Scratching TESTER) manufactured by Shinto Kagaku Co., Ltd., HEIDON (R) -14.
- the upper test piece was a square of 30 mm square
- the lower test piece was a rectangle of 50 mm ⁇ 100 ram
- the upper test piece was pressed on the lower test piece with a load of 200 g
- the upper test piece was slid at a speed of 150 mm / min.
- the dynamic friction coefficient was measured. All shears on the surface to be measured were removed to prevent the force from hitting the other plate.
- Grain-oriented electrical steel sheet 20 ⁇
- Non-oriented electrical steel sheet 10 mm ⁇ / »After inward bending with a round bar (by hand bending), a cellovan tape was applied to the surface of the steel sheet coating and peeled off. The degree of peeling of the coating (including the raised part) was visually judged and evaluated according to the following criteria.
- the steel sheet was put into a constant temperature / humidity test (50 e C, relative humidity: 98%), and after 2 days, the occurrence of redness (occurrence area) was visually evaluated and evaluated according to the following criteria.
- each of the examples of the present invention has a large effect of improving punching properties and sliding properties, and is excellent in adhesion and corrosion resistance.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Electromagnetism (AREA)
- Physics & Mathematics (AREA)
- Power Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Chemical Treatment Of Metals (AREA)
- Laminated Bodies (AREA)
- Soft Magnetic Materials (AREA)
- Manufacturing Of Steel Electrode Plates (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR1020027016928A KR100848021B1 (ko) | 2001-04-12 | 2002-04-10 | 절연피막을 갖는 전자강판 및 절연피막 |
EP02717095A EP1291451A4 (en) | 2001-04-12 | 2002-04-10 | MAGNETIC SHEET HAVING AN INSULATING COATING, AND INSULATING COATING |
US10/297,656 US7226658B2 (en) | 2001-04-12 | 2002-04-10 | Electrical sheet having insulating coating and insulating coating |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2001-113575 | 2001-04-12 | ||
JP2001113575A JP4268344B2 (ja) | 2001-04-12 | 2001-04-12 | 加工性に優れる絶縁被膜付き電磁鋼板 |
Publications (1)
Publication Number | Publication Date |
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WO2002083982A1 true WO2002083982A1 (fr) | 2002-10-24 |
Family
ID=18964774
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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PCT/JP2002/003571 WO2002083982A1 (fr) | 2001-04-12 | 2002-04-10 | Tole magnetique presentant un revetement isolant, et revetement isolant |
Country Status (6)
Country | Link |
---|---|
US (1) | US7226658B2 (ja) |
EP (1) | EP1291451A4 (ja) |
JP (1) | JP4268344B2 (ja) |
KR (1) | KR100848021B1 (ja) |
CN (1) | CN1210442C (ja) |
WO (1) | WO2002083982A1 (ja) |
Families Citing this family (25)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP4360667B2 (ja) * | 2002-08-01 | 2009-11-11 | Jfeスチール株式会社 | 絶縁皮膜付き電磁鋼板 |
JP4380120B2 (ja) * | 2002-08-01 | 2009-12-09 | Jfeスチール株式会社 | 絶縁皮膜付き電磁鋼板 |
JP4987216B2 (ja) * | 2003-06-25 | 2012-07-25 | Jfeスチール株式会社 | 寸法精度に優れた積層コア及びその製造方法 |
JP2005019641A (ja) * | 2003-06-25 | 2005-01-20 | Jfe Steel Kk | 寸法精度に優れた積層コア及びその製造方法 |
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JP6848600B2 (ja) * | 2017-03-29 | 2021-03-24 | 日本製鉄株式会社 | 塗装金属板の製造方法 |
CN107328823A (zh) * | 2017-05-25 | 2017-11-07 | 浙江海洋大学 | 电阻率检测LNAPLs三维运移的方法 |
DE102018209553A1 (de) | 2018-06-14 | 2019-12-19 | Voestalpine Stahl Gmbh | Verfahren zur herstellung von lackbeschichteten elektrobändern und lackbeschichtetes elektroband |
JP7151792B2 (ja) * | 2019-01-16 | 2022-10-12 | 日本製鉄株式会社 | 方向性電磁鋼板の製造方法 |
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CN117497681B (zh) * | 2023-12-29 | 2024-04-05 | 南昌凯捷半导体科技有限公司 | 一种Mini-LED芯片及其制作方法 |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS61183480A (ja) * | 1985-02-09 | 1986-08-16 | Sumitomo Metal Ind Ltd | 電磁鋼板に絶縁皮膜を形成する方法 |
JPH07286283A (ja) * | 1994-04-18 | 1995-10-31 | Kawasaki Steel Corp | 溶接性およびオイルレス打抜性に優れた電気絶縁被膜を有する電磁鋼板 |
JPH07331453A (ja) * | 1994-06-08 | 1995-12-19 | Kawasaki Steel Corp | 溶接性およびオイルレス打抜性に優れた電気絶縁被膜を有する電磁鋼板 |
Family Cites Families (23)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4104225A (en) * | 1971-11-26 | 1978-08-01 | Imperial Chemical Industries Limited | Method of making a coating composition containing a fluorocarbon polymer resin and an aluminum containing binder |
IT1029613B (it) * | 1974-10-09 | 1979-03-20 | Terni Societa Per L Ind | Procedimento per la produzione di lamierino magnetico ad alta permea bilita |
GB1537851A (en) * | 1975-07-29 | 1979-01-04 | Ici Ltd | Coating compositions |
JPS535800A (en) * | 1976-07-05 | 1978-01-19 | Kawasaki Steel Co | Highhmagneticcflux density oneeway siliconnsteellfolstellite insulator film and method of formation thereof |
US4140645A (en) * | 1978-06-12 | 1979-02-20 | Corning Glass Works | Glasses and glass-ceramics suitable for induction heating |
JPS6038068A (ja) * | 1983-08-10 | 1985-02-27 | Sumitomo Metal Ind Ltd | 電磁鋼板に絶縁皮膜を形成する方法 |
US4701345A (en) * | 1986-03-11 | 1987-10-20 | Markel Corporation | Process for applying polymeric coatings, and resulting coated articles |
US4800661A (en) * | 1986-05-20 | 1989-01-31 | Toshiba Heating Appliances Co., Ltd. | Electric iron |
JPS63193965A (ja) * | 1987-02-06 | 1988-08-11 | Mitsui Toatsu Chem Inc | 耐熱性プレコ−トメタル用被覆材 |
DE3720217A1 (de) * | 1987-06-17 | 1988-12-29 | Metallgesellschaft Ag | Verfahren zur erzeugung elektrisch isolierender ueberzuege auf metalloberflaechen |
JPH07116507B2 (ja) * | 1989-02-23 | 1995-12-13 | 日本鋼管株式会社 | 無方向性電磁鋼板の製造方法 |
US5573846A (en) * | 1991-10-24 | 1996-11-12 | Norton Pampus Gmbh | Polyfluorocarbon coated metal bearing |
JP2585936B2 (ja) * | 1991-11-15 | 1997-02-26 | 住友電気工業株式会社 | 弗素樹脂被覆物の製造方法 |
IT1270622B (it) * | 1994-07-14 | 1997-05-07 | Lambda Srl | Procedimento per l'applicazione di rivestimenti antiaderenti e termoresistenti a lamiere di alluminio |
CA2224667C (en) * | 1997-12-12 | 2007-07-03 | Kawasaki Steel Corporation | Solvent-resistant electrical steel sheet capable of stress relief annealing and process |
US6191510B1 (en) * | 1997-12-19 | 2001-02-20 | 3M Innovative Properties Company | Internally damped stator, rotor, and transformer and a method of making |
WO1999045044A1 (fr) * | 1998-03-06 | 1999-09-10 | Daikin Industries, Ltd. | Materiau adhesif a base de composes fluores et stratifie fabrique dans ce materiau |
US6232372B1 (en) * | 1998-03-18 | 2001-05-15 | E. I. Du Pont De Nemours And Company | Multicomponent particles of fluoropolymer and high temperature resistant non-dispersed polymer binder |
TWI221861B (en) * | 1998-04-22 | 2004-10-11 | Toyo Boseki | Agent for treating metallic surface, surface-treated metal material and coated metal material |
JP3799878B2 (ja) * | 1998-07-16 | 2006-07-19 | 住友金属工業株式会社 | 電磁鋼板およびその製造方法電磁鋼板の製造方法 |
US6794027B1 (en) * | 1998-08-24 | 2004-09-21 | Daikin Industries, Ltd. | Thin coating film comprising fluorine-containing polymer and method of forming same |
US6291054B1 (en) * | 1999-02-19 | 2001-09-18 | E. I. Du Pont De Nemours And Company | Abrasion resistant coatings |
EP1245657B1 (en) * | 1999-09-08 | 2006-11-08 | Daikin Industries, Ltd. | Fluorochemical adhesive material and layered product obtained with the same |
-
2001
- 2001-04-12 JP JP2001113575A patent/JP4268344B2/ja not_active Expired - Fee Related
-
2002
- 2002-04-10 US US10/297,656 patent/US7226658B2/en not_active Expired - Lifetime
- 2002-04-10 KR KR1020027016928A patent/KR100848021B1/ko active IP Right Grant
- 2002-04-10 CN CNB028020618A patent/CN1210442C/zh not_active Expired - Fee Related
- 2002-04-10 EP EP02717095A patent/EP1291451A4/en not_active Withdrawn
- 2002-04-10 WO PCT/JP2002/003571 patent/WO2002083982A1/ja active Application Filing
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS61183480A (ja) * | 1985-02-09 | 1986-08-16 | Sumitomo Metal Ind Ltd | 電磁鋼板に絶縁皮膜を形成する方法 |
JPH07286283A (ja) * | 1994-04-18 | 1995-10-31 | Kawasaki Steel Corp | 溶接性およびオイルレス打抜性に優れた電気絶縁被膜を有する電磁鋼板 |
JPH07331453A (ja) * | 1994-06-08 | 1995-12-19 | Kawasaki Steel Corp | 溶接性およびオイルレス打抜性に優れた電気絶縁被膜を有する電磁鋼板 |
Non-Patent Citations (1)
Title |
---|
See also references of EP1291451A4 * |
Also Published As
Publication number | Publication date |
---|---|
JP2002309379A (ja) | 2002-10-23 |
JP4268344B2 (ja) | 2009-05-27 |
EP1291451A4 (en) | 2008-12-24 |
US20030175524A1 (en) | 2003-09-18 |
CN1463301A (zh) | 2003-12-24 |
KR20030024691A (ko) | 2003-03-26 |
KR100848021B1 (ko) | 2008-07-23 |
CN1210442C (zh) | 2005-07-13 |
US7226658B2 (en) | 2007-06-05 |
EP1291451A1 (en) | 2003-03-12 |
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