WO2024135441A1 - 絶縁被膜付き電磁鋼板の製造方法 - Google Patents

絶縁被膜付き電磁鋼板の製造方法 Download PDF

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Publication number
WO2024135441A1
WO2024135441A1 PCT/JP2023/044276 JP2023044276W WO2024135441A1 WO 2024135441 A1 WO2024135441 A1 WO 2024135441A1 JP 2023044276 W JP2023044276 W JP 2023044276W WO 2024135441 A1 WO2024135441 A1 WO 2024135441A1
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Prior art keywords
water
resin
steel sheet
based paint
mass
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Ceased
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PCT/JP2023/044276
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English (en)
French (fr)
Japanese (ja)
Inventor
直樹 村松
武士 松田
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JFE Steel Corp
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JFE Steel Corp
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Application filed by JFE Steel Corp filed Critical JFE Steel Corp
Priority to KR1020257015294A priority Critical patent/KR20250086726A/ko
Priority to CN202380086737.7A priority patent/CN120380196A/zh
Priority to JP2024565824A priority patent/JP7772257B2/ja
Priority to EP23906806.7A priority patent/EP4600404A1/en
Publication of WO2024135441A1 publication Critical patent/WO2024135441A1/ja
Priority to MX2025007274A priority patent/MX2025007274A/es
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08Anti-corrosive paints
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    • C23COATING 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
    • C23CCOATING 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
    • C23C26/00Coating not provided for in groups C23C2/00 - C23C24/00
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    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D201/00Coating compositions based on unspecified macromolecular compounds
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    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/02Emulsion paints including aerosols
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    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40Additives
    • C09D7/60Additives non-macromolecular
    • C09D7/61Additives non-macromolecular inorganic
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    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40Additives
    • C09D7/60Additives non-macromolecular
    • C09D7/63Additives non-macromolecular organic
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    • C21METALLURGY OF IRON
    • C21DMODIFYING 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
    • C21D8/00Modifying the physical properties of ferrous metals or ferrous alloys by deformation combined with, or followed by, heat treatment
    • C21D8/12Modifying the physical properties of ferrous metals or ferrous alloys by deformation combined with, or followed by, heat treatment during manufacturing of articles with special electromagnetic properties
    • C21D8/1277Modifying the physical properties of ferrous metals or ferrous alloys by deformation combined with, or followed by, heat treatment during manufacturing of articles with special electromagnetic properties involving a particular surface treatment
    • C21D8/1283Application of a separating or insulating coating
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    • C21METALLURGY OF IRON
    • C21DMODIFYING 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
    • C21D9/00Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
    • C21D9/46Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for sheet metals
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    • C23COATING 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
    • C23CCOATING 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
    • C23C22/00Chemical 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
    • C23C22/05Chemical 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 using aqueous solutions
    • C23C22/06Chemical 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 using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/24Chemical 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 using aqueous solutions using aqueous acidic solutions with pH less than 6 containing hexavalent chromium compounds
    • C23C22/26Chemical 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 using aqueous solutions using aqueous acidic solutions with pH less than 6 containing hexavalent chromium compounds containing also organic compounds
    • C23C22/28Macromolecular compounds
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    • C23COATING 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
    • C23CCOATING 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
    • C23C22/00Chemical 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
    • C23C22/05Chemical 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 using aqueous solutions
    • C23C22/06Chemical 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 using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/24Chemical 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 using aqueous solutions using aqueous acidic solutions with pH less than 6 containing hexavalent chromium compounds
    • C23C22/33Chemical 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 using aqueous solutions using aqueous acidic solutions with pH less than 6 containing hexavalent chromium compounds containing also phosphates
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C22/00Chemical 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
    • C23C22/05Chemical 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 using aqueous solutions
    • C23C22/06Chemical 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 using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/48Chemical 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 using aqueous solutions using aqueous acidic solutions with pH less than 6 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
    • C23C22/50Treatment of iron or alloys based thereon
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C22/00Chemical 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
    • C23C22/73Chemical 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 characterised by the process
    • C23C22/74Chemical 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 characterised by the process for obtaining burned-in conversion coatings
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01FMAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
    • H01F1/01Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
    • H01F1/03Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
    • H01F1/12Magnets 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
    • H01F1/14Magnets 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
    • H01F1/147Alloys characterised by their composition
    • H01F1/14766Fe-Si based alloys
    • H01F1/14775Fe-Si based alloys in the form of sheets
    • H01F1/14783Fe-Si based alloys in the form of sheets with insulating coating
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01FMAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
    • H01F1/01Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
    • H01F1/03Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
    • H01F1/12Magnets 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
    • H01F1/14Magnets 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
    • H01F1/16Magnets 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 in the form of sheets
    • H01F1/18Magnets 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 in the form of sheets with insulating coating
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C22/00Chemical 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

Definitions

  • the present invention relates to a method for manufacturing electrical steel sheets with insulating coating.
  • Insulating coated electrical steel sheet naturally has excellent magnetic properties, which are its basic characteristic, but various other properties are also required in the manufacturing process of motors, transformers, etc. Examples of properties required in the manufacturing process of such products include punchability, weldability (welding of end faces), coating adhesion, and corrosion resistance. It is a well-known fact that adding a resin component to the insulating coating is effective in improving punchability, but the addition of resin can cause blowholes during welding, so achieving both punchability and weldability has been a challenge.
  • Patent Document 1 describes a method for manufacturing "electrical steel sheet with an insulating coating that has excellent weldability and punchability, characterized by applying a water-based coating liquid containing a resin and an inorganic component to the surface of the electrical steel sheet, and then heating and baking the coating from the steel sheet side.”
  • Patent Document 1 Although weldability and punchability were improved, there was still room for improvement in terms of achieving both weldability and punchability under stricter evaluation conditions.
  • the present invention aims to provide a method for manufacturing an insulating coated electrical steel sheet that has excellent punchability and weldability under stricter evaluation conditions.
  • the inventors After extensive research to achieve this objective, the inventors have newly discovered that by maintaining within an appropriate range the viscosity of the water-based paint containing the resin and inorganic components used to form the insulating coating, it is possible to obtain an insulating coated electrical steel sheet that is excellent in both punchability and weldability under stricter evaluation conditions. It has been found that the effect of improving punchability and weldability by maintaining within an appropriate range the viscosity of the water-based paint applied to the electrical steel sheet is not limited to the case of heating from the steel sheet side by induction heating as described in Patent Document 1, but can also be obtained when heating is performed from the surface of the coating film formed by the water-based paint, as in a gas furnace or electric furnace.
  • the gist and configuration of the present invention which has been completed based on the above findings, are as follows. [1] preparing a water-based paint; applying the water-based paint to a surface of an electrical steel sheet and drying it by heating to form an insulating coating; having The water-based paint contains a resin, an inorganic component, an optional organic reducing agent, an optional boron compound (B compound), and water; 50% by mass or more of the resin is composed of one or both of an emulsion resin and a dispersion resin, 4.
  • [4] A method for producing an electrical steel sheet with an insulating coating according to any one of [1] to [3], in which one or both of the emulsion resin and the dispersion resin in the water-based paint have a particle size of 30 nm or more.
  • the manufacturing method of the insulating coated electrical steel sheet of the present invention makes it possible to manufacture insulating coated electrical steel sheet that is excellent in both punchability and weldability under stricter evaluation conditions.
  • the method for manufacturing an electrical steel sheet with an insulating coating includes the steps of preparing a water-based paint, and applying the water-based paint to the surface of the electrical steel sheet and drying it by heating to form an insulating coating.
  • the water-based paint contains a resin, an inorganic component, an optional organic reducing agent, an optional B compound, and water, and is characterized in that 50% or more by mass of the resin is composed of one or both of an emulsion resin and a dispersion resin, and the water-based paint has a viscosity of 1.0 mPa ⁇ s or more.
  • the electromagnetic steel sheet that serves as the base for the insulating coating there are no particular restrictions on the electromagnetic steel sheet that serves as the base for the insulating coating, but it is preferable to adjust the composition appropriately according to the desired characteristics. For example, increasing resistivity is effective in improving iron loss, so it is preferable to add resistivity-improving components such as Si, Al, Mn, Cr, P, and Ni. The ratio of these components can be determined according to the desired magnetic properties.
  • the C and S contained in electrical steel sheets are elements that are detrimental to weldability, and it is also desirable to reduce their content in terms of magnetic properties. Therefore, it is preferable that the C content in electrical steel sheets be 0.01 mass% or less. It is also preferable that the S content in electrical steel sheets be 0.01 mass% or less. There are no particular restrictions on the other trace components, segregation elements such as Sb and Sn, and unavoidable impurities contained in electrical steel sheets.
  • the manufacturing method of the electromagnetic steel sheet there are no particular restrictions on the manufacturing method of the electromagnetic steel sheet, and various conventionally known methods can be applied. There are also no particular restrictions on the surface roughness of the steel sheet, but when emphasis is placed on the space factor, it is preferable that the three-dimensional surface roughness SRa be 0.5 ⁇ m or less. Furthermore, there are no particular restrictions on the final thickness of the steel sheet, and various thicknesses can be applied, but from the viewpoint of magnetic properties, it is preferable that the thickness be 0.8 mm or less.
  • Water-based paints contain resins and inorganic components. These resins and inorganic components have the property of being soluble or dispersible in water. Water-based paints may also contain one or both of an organic reducing agent and a B compound. Water-based paints may use any type of coating treatment liquid, such as a coating treatment liquid containing at least a chromate and a resin, a coating treatment liquid containing at least a phosphate and a resin, or a coating treatment liquid containing at least an inorganic colloid and a resin. Water-based paints may also contain various components to improve heat resistance or corrosion resistance.
  • the type of resin contained in the water-based paint is not particularly limited, and one or more selected from acrylic resin, epoxy resin, urethane resin, phenol resin, styrene resin, amide resin, imide resin, urea resin, vinyl acetate resin, alkyd resin, polyolefin resin, and polyester resin may be used, and these may be used as a single substance, a copolymer, or a mixture.
  • the total resin amount (solid content) in the water-based paint 50 mass% or more is resin with particle size, that is, one or both of emulsion resin and dispersion resin.
  • the mass ratio of one or both of emulsion resin and dispersion resin in the resin contained in the water-based paint is 50 mass% or more and 100 mass% or less, it means that the mass ratio of completely water-soluble resin without particle size is 0 mass% or more and 50 mass% or less. If the mass ratio of completely water-soluble resin without particle size exceeds 50 mass%, the effect of improving punchability is not obtained satisfactorily.
  • so-called monomers such as water-soluble acrylic acid, which are components of the resin, are also included in the calculation of "resin".
  • the emulsion resin and/or dispersion resin in the water-based paint preferably have a particle size of 30 nm or more. If the particle size of the emulsion resin and/or dispersion resin is 30 nm or more, the resin area that adheres to the die end face and covers the die tip during punching is suitable, the adhesive wear suppression effect between the die end face and the workpiece is suitable, and punching properties are favorable. There is no particular upper limit on the particle size of the resin, but if the space factor is important, it is preferable that the particle size of the resin be 1 ⁇ m or less. The particle size of the resin can be measured by dynamic light scattering in accordance with JIS 8828:2013.
  • the solid mass ratio of the resin to the total mass of the resin, inorganic components, organic reducing agent, and B compound converted into solid content is preferably 0.5 mass% or more and 50 mass% or less.
  • the solid mass ratio of the resin is 0.5 mass% or more, the above-mentioned effect of improving punchability (adhesive wear suppression effect) is preferably obtained.
  • the solid mass ratio of the resin is 50 mass% or less, the amount of organic matter that decomposes and vaporizes during welding is suitable, blowholes in the weld bead can be suppressed, and weldability is preferably obtained. It is even more preferable that the solid mass ratio of the resin is 40 mass% or less.
  • Inorganic components contained in the water-based paint include Cr compounds, P compounds, and Si compounds.
  • Cr compounds include chromates and dichromates containing at least one metal selected from Ca, Mg, Zn, K, Na, Al, etc., and one or more of these can be used.
  • Phosphates can be used as P compounds, and examples of these include aluminum phosphate, magnesium phosphate, calcium phosphate, iron phosphate, and zinc phosphate, and one or more of these can be used.
  • Si compounds include colloidal silica, fumed silica, and plate-like silica, and one or more of these can be used. Colloidal silica, fumed silica, and plate-like silica exist in the form of particles in the insulating coating. Multiple types of inorganic compounds may also be contained.
  • the solid mass ratio of the inorganic components to the total mass of the resin, inorganic components, organic reducing agent, and B compound converted into solid content is preferably 30 mass% or more, and more preferably 60 mass% or more. Furthermore, if the ratio of the inorganic components is too high, there is a concern that the punchability may deteriorate, so the mass ratio is preferably 80 mass% or less.
  • the water-based paint contains an organic reducing agent.
  • an organic reducing agent By including an organic reducing agent, the reduction reaction of chromium can be favorably promoted.
  • the type of organic reducing agent is not particularly limited, but it is preferable to use at least one selected from diols and sugars. In particular, it is more preferable to use one or more diols selected from ethylene glycol and 1,4-butanediol, and one or more sugars selected from glycerin, polyethylene glycol, sucrose, lactose, sucrose, glucose, and fructose.
  • the solid mass ratio of the organic reducing agent to the total mass of the resin, inorganic components, organic reducing agent, and B compound converted into solids is preferably 10 mass% or more. Furthermore, if the content of the organic reducing agent is too high, the coating properties after annealing will deteriorate, so the mass ratio is preferably 30 mass% or less.
  • the water-based paint contains a B compound.
  • B compounds include boric acid, orthoboric acid, metaboric acid, tetraboric acid, sodium metaborate, sodium tetraborate, etc., and these can be used alone or in combination.
  • the B compound is not limited to these, and may be, for example, a compound that dissolves in water to generate borate ions, and the borate ions may be linearly or cyclically polymerized.
  • the solid mass ratio of B compound to the total mass of the resin, inorganic components, organic reducing agent, and B compound converted into solids is preferably 5 mass% or more. Furthermore, if the content of B compound is too high, the coating properties after annealing will deteriorate, so this mass ratio is preferably 30 mass% or less.
  • the water-based paint has a viscosity of 1.0 mPa ⁇ s or more. If the viscosity of the water-based paint is less than 1.0 mPa ⁇ s, the resin particles settle in the paint and tend to form non-uniform aggregates, making it difficult to obtain sufficient weldability under stricter evaluation conditions. The cause of the deterioration of weldability due to non-uniform aggregates is not clear, but it is thought that the presence of non-uniform aggregates of resin particles makes it difficult to remove low-boiling point components in the water-based paint (coating film) whether the steel plate side or the coating film surface side is heated.
  • the resin particles can be uniformly dispersed in the paint, thereby suppressing the formation of aggregates.
  • the viscosity of the water-based paint is preferably 40 mPa ⁇ s or less, and more preferably 10 mPa ⁇ s or less. If the viscosity is 10 mPa ⁇ s or less, streak-like coating defects called roping can be suitably suppressed when forming a coating on a steel plate.
  • the solids concentration of the water-based paint may be adjusted to achieve the desired viscosity, or a viscosity modifier may be added.
  • a viscosity modifier There are no particular restrictions on the type of viscosity modifier, and commonly used ones such as acrylic polymers and urethane-modified polyethers may be used.
  • the viscosity of the water-based paint in this invention is a value measured after mixing each component in a specified ratio and adjusting to the desired solid concentration.
  • the viscosity is also a value measured in accordance with JIS K 6901:2021. For example, it can be measured using a BM type viscometer (manufactured by Tokyo Keiki Co., Ltd.) at a test temperature of 25°C.
  • the method for applying the water-based paint can be any method that allows the water-based paint to be applied to the steel plate, and various methods can be applied, such as the roll coater method, bar coater method, air knife method, and spray coater method.
  • the heating temperature i.e., the maximum sheet temperature
  • the heating temperature may be the temperature required to form the insulating coating, but since a water-based paint is used, it is preferable to set it to 100°C or higher, and more preferably 150°C or higher. By setting it to 100°C or higher, residual water can be suitably suppressed.
  • the maximum sheet temperature is preferably set to 350°C or lower. By setting it to 350°C or lower, thermal decomposition of the resin can be suitably suppressed.
  • the coating is preferably heated from the steel sheet side (the lower layer of the coating). Heating from the lower layer of the coating provides good punchability and weldability. The reason for this is unclear, but the inventors believe it to be as follows. 1) When heating is applied from the bottom of the coating, convection occurs within the uncoagulated coating film, and resins that are not completely dissolved but have a particulate form, such as emulsion resins and dispersion resins, are concentrated near the surface layer, increasing the amount of resin in the outermost layer and improving punchability. 2) When heating is applied from the surface of the coating, the surface dries first and low-boiling point components tend to remain inside the coating, which turn into gas during welding and cause blowholes. However, when heating is applied from the steel plate side (lower layer of the coating), the low-boiling point components are effectively removed from the paint film, resulting in stable weldability.
  • the weight of the insulating coating is preferably 0.05 g/ m2 or more in dry weight. When the weight of the insulating coating is 0.05 g/ m2 or more, the coating is applied uniformly and the coating performance is stable.
  • the weight of the insulating coating is preferably 7.0 g/ m2 or less in dry weight. By setting the weight to 7.0 g/ m2 or less, the coating adhesion can be favorably obtained.
  • the resins, inorganic components, organic reducing agents, and B compounds shown in Tables 1 and 2 were added to deionized water in the amounts (solids content equivalent) shown in Tables 1 and 2, and mixed to prepare water-based paints.
  • ethylene glycol used as an organic reducing agent is liquid at room temperature, but the content was calculated as solids content.
  • the solids concentration of the water-based paint was 3% by mass.
  • thickener A-10H manufactured by Toa Gosei Co., Ltd.
  • Table 1 shows that the examples of the invention in which the viscosity of the water-based paint is 1 mPa ⁇ s or more are superior to the comparative examples in terms of appearance, weldability, and punchability. Comparing Tables 1 and 2, it can be seen that when heating is performed from the bottom layer of the coating by induction heating, the weldability is superior to heating by a gas furnace, but even in the case of a gas furnace, it can be seen that performance can be improved by controlling the viscosity of the water-based paint. From this, it is clear that the effects of the present invention can be obtained regardless of the heating method.

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PCT/JP2023/044276 2022-12-23 2023-12-11 絶縁被膜付き電磁鋼板の製造方法 Ceased WO2024135441A1 (ja)

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KR1020257015294A KR20250086726A (ko) 2022-12-23 2023-12-11 절연 피막이 형성된 전기 강판의 제조 방법
CN202380086737.7A CN120380196A (zh) 2022-12-23 2023-12-11 带绝缘被膜的电磁钢板的制造方法
JP2024565824A JP7772257B2 (ja) 2022-12-23 2023-12-11 絶縁被膜付き電磁鋼板の製造方法
EP23906806.7A EP4600404A1 (en) 2022-12-23 2023-12-11 Method for manufacturing electromagnetic steel sheet with insulating film
MX2025007274A MX2025007274A (es) 2022-12-23 2025-06-19 Metodo de produccion de chapa de acero electrico con recubrimiento aislante

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003147543A (ja) * 2001-11-08 2003-05-21 Toshio Odajima 電磁鋼板用クロムフリー表面処理剤及び表面処理電磁鋼板
JP2011246783A (ja) * 2010-05-28 2011-12-08 Jfe Steel Corp 無機質絶縁被膜付き電磁鋼板

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JP4221933B2 (ja) 2002-01-28 2009-02-12 Jfeスチール株式会社 溶接性および打抜性に優れる絶縁被膜付き電磁鋼板の製造方法
KR100816695B1 (ko) * 2004-03-19 2008-03-27 제이에프이 스틸 가부시키가이샤 절연 피막을 갖는 전자 강판

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003147543A (ja) * 2001-11-08 2003-05-21 Toshio Odajima 電磁鋼板用クロムフリー表面処理剤及び表面処理電磁鋼板
JP2011246783A (ja) * 2010-05-28 2011-12-08 Jfe Steel Corp 無機質絶縁被膜付き電磁鋼板

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
SAKAI YOSHIYUKI , TSUYOSHI KITAMOTO: "The Fundamental and the Technical Trend of the Water-bone Resin for Paints ", JOURNAL OF THE JAPAN SOCIETY OF COLOUR MATERIAL, vol. 77, no. 4, 1 January 2004 (2004-01-01), pages 169 - 176, XP093185332, DOI: 10.4011/shikizai1937.77.169 *

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