WO2016171104A1 - Tôle d'acier électromagnétique à revêtement isolant et agent de traitement de surface aqueux - Google Patents

Tôle d'acier électromagnétique à revêtement isolant et agent de traitement de surface aqueux Download PDF

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Publication number
WO2016171104A1
WO2016171104A1 PCT/JP2016/062276 JP2016062276W WO2016171104A1 WO 2016171104 A1 WO2016171104 A1 WO 2016171104A1 JP 2016062276 W JP2016062276 W JP 2016062276W WO 2016171104 A1 WO2016171104 A1 WO 2016171104A1
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Prior art keywords
fluoropolymer
steel sheet
insulating coating
sheet
electrical steel
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PCT/JP2016/062276
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English (en)
Japanese (ja)
Inventor
俊 齋藤
将崇 相川
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旭硝子株式会社
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Priority to JP2017514114A priority Critical patent/JP6733665B2/ja
Publication of WO2016171104A1 publication Critical patent/WO2016171104A1/fr

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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
    • C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
    • C21D9/46—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for sheet metals
    • 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
    • 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
    • H01F1/16—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 in the form of sheets
    • H01F1/18—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 in the form of sheets with insulating coating

Definitions

  • the present invention relates to an electrical steel sheet with an insulating coating that is excellent in water resistance and rust prevention under a high temperature and humidity environment, and has excellent adhesion of the insulating coating and the appearance of the coating, a motor having the electrical steel sheet with the insulating coating, and an electrical steel sheet
  • the present invention relates to a water-based surface treatment agent used for forming an insulating film on the surface.
  • an electromagnetic steel sheet having a chromate film on its surface is used as an electromagnetic steel sheet that is not easily corroded by oxidation.
  • chromate films include reactive chromate treatment methods (methods using surface treatment agents containing chromium such as chromate chromate and phosphate chromate), and coating chromate treatment methods (chromate or surface containing chromate and silica). And a film formed by a method using a treatment agent).
  • an electrical steel sheet having an electrically insulating coating on its surface has also been proposed.
  • an electrical steel sheet with an insulating coating having an insulating coating containing a fluoropolymer on its surface has been proposed (see Patent Documents 1 and 2).
  • the insulating coating described in Patent Document 1 has low adhesion to the electrical steel sheet and is easily peeled off. As a result, there is a problem that the electrical rust resistance of the electrical steel sheet with the insulating coating is inferior in a high-temperature wet environment.
  • the insulating coating described in Patent Document 2 has low water resistance, and in particular, there is a problem that the rust prevention property of the electrical steel sheet with the insulating coating is inferior in a high-temperature wet environment. Furthermore, the insulating film is required to have excellent appearance characteristics.
  • An object of the present invention is to provide an electrical steel sheet with an insulation coating that is excellent in water resistance and rust prevention under a high temperature and humidity environment, has excellent adhesion to the electrical steel sheet of the insulation coating, and has excellent appearance characteristics of the insulation coating. Is to provide.
  • Another object of the present invention is to provide a motor having a magnetic steel sheet with an insulating coating excellent in the above-mentioned various characteristics, and an aqueous surface treating agent used for forming such an insulating coating.
  • the present invention has the following gist.
  • An electrical steel sheet with an insulating coating comprising an electrical steel sheet, and a fluoropolymer having units based on fluoroolefins and an insulating coating containing a metal salt disposed on the electrical steel sheet, wherein the fluoropolymer is An electrical steel sheet with an insulating coating satisfying the following requirements 1 and 2.
  • Requirement 1 When the fluoropolymer is formed into a sheet, the water vapor transmission rate per 1 ⁇ m of film thickness of the fluoropolymer sheet is 0.01 to 5 g / m 2 ⁇ day.
  • Requirement 2 When the fluoropolymer is formed into a sheet, the oxygen permeability per 1 ⁇ m thickness of the fluoropolymer sheet is less than 0.2 mol / m 2 ⁇ s ⁇ Pa. (2) The electrical steel sheet with an insulating coating according to (1), wherein the fluoropolymer further satisfies the following requirement 3.
  • Requirement 3 When the fluoropolymer is formed into a sheet shape, the carbon dioxide permeability per 1 ⁇ m of film thickness of the fluoropolymer sheet is less than 0.1 mol / m 2 ⁇ s ⁇ Pa.
  • the fluorinated polymer is vinyl ether, allyl ether or vinyl carboxylate, and has a unit based on the monomer A having an alicyclic alkyl group, The electrical steel sheet with an insulation film as described.
  • the fluorine-containing polymer is a vinyl ether, allyl ether or vinyl carboxylate, and has a unit based on the monomer B having at least one crosslinkable group selected from a hydroxyl group, a carboxy group and an amino group.
  • the metal salt is a metal salt of at least one inorganic acid selected from phosphoric acid, nitric acid, carbonic acid, sulfuric acid, hexafluorosilicic acid, hexafluorotitanic acid, and hexafluorozirconic acid, or formic acid, acetic acid
  • Any one of (10) to (12), wherein the metal of the metal salt is Li, Al, Mg, Ca, Sr, Ti, Ni, Mn, Co, Zr, Fe, Cu, or Ag.
  • an electrical steel sheet with an insulation coating that is excellent in water resistance and rust prevention under a high temperature and humidity environment, has excellent adhesion to the electrical steel sheet of the insulation coating, and also has excellent appearance characteristics of the insulation coating. Is done.
  • the water-type surface treating agent which can form easily the motor which has the electromagnetic steel plate with an insulating film which has the said outstanding characteristic, and the insulating coating concerning the surface of an electromagnetic steel plate is provided.
  • the “unit” constituting the polymer means a portion derived from a monomer that is present in the polymer and constitutes the polymer.
  • the unit derived from the monomer resulting from addition polymerization of a monomer having a carbon-carbon unsaturated double bond is a divalent unit generated by cleavage of the unsaturated double bond.
  • what unitally converted the structure of a unit after polymer formation is also called a unit.
  • a unit derived from an individual monomer is referred to as a name obtained by adding “unit” to the monomer name.
  • a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
  • the kind of the electrical steel sheet contained in the electrical steel sheet with an insulating coating is not particularly limited, and a known electrical steel sheet can be used.
  • the magnetism of the electrical steel sheet may be any of directionality, non-direction, or bidirectional.
  • a forsterite film or a phosphate-based film that generates tension may be present on the surface.
  • the chemical composition of the electrical steel sheet is not particularly limited, and if it is a grain oriented electrical steel sheet, for example, the chemical composition of Si: 2 to 4 mass%, Mn: ⁇ 0.4 mass%, Al: ⁇ 0.1 mass%.
  • the thickness of the electromagnetic steel sheet is not particularly limited, and is, for example, about 0.05 to 1.0 mm.
  • the insulating coating which an electromagnetic steel plate with an insulating coating has is a sheet-like (film-like) layer disposed on the electromagnetic steel plate.
  • the thickness of the insulating coating is usually preferably from 0.3 to 3.0 ⁇ m, more preferably from 0.5 to 1.5 ⁇ m.
  • the insulating coating is a coating containing a fluoropolymer having a unit based on fluoroolefin and a metal salt.
  • the fluorine-containing polymer contained in the insulating film exhibits predetermined characteristics. Specifically, first, the fluoropolymer satisfies the following requirement 1. That is, the insulating coating contains a fluorine-containing polymer that exhibits a predetermined water vapor transmission rate when formed into a sheet.
  • Requirement 1 When the fluoropolymer sheet is formed into a sheet, the water vapor transmission rate per 1 ⁇ m thickness of the fluoropolymer sheet is 0.01 to 5 g / m 2 ⁇ day.
  • the water vapor transmission rate is particularly preferably 0.01 to 2.5 g / m 2 ⁇ day, and more preferably 0.01 to 1.9 g / m 2 ⁇ day.
  • the method of making the fluoropolymer into a sheet is not particularly limited.
  • a method of applying a solution containing the fluoropolymer in a sheet (film) and removing the solvent as necessary examples include a method in which a polymer is melted to form a sheet (film) by various molding methods (for example, extrusion molding).
  • a sheet having a film thickness of 60 ⁇ m is prepared as the fluoropolymer sheet.
  • a fluoropolymer sheet also has a crosslinked structure.
  • the crosslinkable group is used.
  • the water vapor transmission rate is measured using a fluoropolymer sheet prepared using a fluoropolymer having the above and a crosslinking agent. This also applies to the fluoropolymer sheet used for measuring oxygen permeability and carbon dioxide permeability.
  • the water vapor transmission rate of the fluoropolymer sheet is a film thickness of 60 ⁇ m measured in accordance with JIS Z 0208 B conditions (temperature 40 ° C. ⁇ 0.5 ° C., humidity 90% ⁇ 2%).
  • the value obtained by converting the value of water vapor permeability of the fluoropolymer sheet per 1 ⁇ m thickness that is, the value obtained by dividing the value of water vapor permeability of the fluoropolymer sheet having a thickness of 60 ⁇ m by 60.
  • the fluoropolymer satisfies the following requirement 2. That is, the insulating coating contains a fluorine-containing polymer that exhibits a predetermined oxygen permeability when formed into a sheet.
  • Requirement 2 When the fluoropolymer is formed into a sheet, the oxygen permeability per 1 ⁇ m thickness of the fluoropolymer sheet is less than 0.2 mol / m 2 ⁇ s ⁇ Pa.
  • Oxygen permeability in particular, is preferably not more than 0.1mol / m 2 ⁇ s ⁇ Pa , more preferably at most 0.05mol / m 2 ⁇ s ⁇ Pa .
  • the lower limit is not particularly limited, and is more than 0.00 mol / m 2 ⁇ s ⁇ Pa.
  • the production method and definition of the fluoropolymer sheet are as described above.
  • the oxygen permeability of the fluoropolymer sheet is the oxygen permeability value of a fluoropolymer sheet having a film thickness of 60 ⁇ m measured in accordance with JIS K 7126-1 per 1 ⁇ m of film thickness.
  • the converted value that is, the value obtained by dividing the oxygen permeability value of the fluoropolymer sheet having a film thickness of 60 ⁇ m by 60.
  • the fluoropolymer preferably satisfies the following requirement 3.
  • Requirement 3 When the fluoropolymer sheet is formed into a sheet, the carbon dioxide permeability per 1 ⁇ m thickness of the fluoropolymer sheet is less than 0.1 mol / m 2 ⁇ s ⁇ Pa.
  • the carbon dioxide permeability is preferably 0.08 mol / m 2 ⁇ s ⁇ Pa or less, and more preferably 0.05 mol / m 2 ⁇ s ⁇ Pa or less.
  • the lower limit is not particularly limited, and is more than 0.00 mol / m 2 ⁇ s ⁇ Pa.
  • the production method and definition of the fluoropolymer sheet are as described above.
  • the carbon dioxide permeability of the fluoropolymer sheet is the value of the carbon dioxide permeability of the fluoropolymer sheet having a film thickness of 60 ⁇ m measured in accordance with JIS K 7126-1. This is a value obtained by dividing the value of carbon dioxide permeability of the fluoropolymer sheet having a film thickness of 60 ⁇ m by 60.
  • the fluoroolefin is a compound in which one or more hydrogen atoms of a hydrocarbon-based olefin (general formula C n H 2n ) are substituted with a fluorine atom.
  • the fluoroolefin has preferably 2 to 8 carbon atoms, more preferably 2 to 6 carbon atoms.
  • the number of fluorine atoms in the fluoroolefin is preferably 2 or more, more preferably 3-4.
  • one or more hydrogen atoms not substituted with fluorine atoms may be substituted with chlorine atoms.
  • the unit based on the fluoroolefin in the fluoropolymer is preferably a unit based on vinylidene fluoride, trifluoroethylene, chlorotrifluoroethylene, tetrafluoroethylene, or hexafluoropropylene. From the viewpoint of alternating polymerizability, chlorotrifluoroethylene or tetrafluoroethylene is particularly preferred.
  • the fluoropolymer may have a unit based on a fluoromonomer other than a unit based on a fluoroolefin.
  • the fluorine-containing monomer include trifluoroethyl acrylate, pentafluoropropyl acrylate, perfluorocyclohexyl acrylate, trifluoroethyl methacrylate, pentafluoropropyl methacrylate, and perfluorocyclohexyl methacrylate. It is done.
  • the content of the monomer based on fluoroolefin is preferably 20 to 80 mol%, preferably 30 to 70 mol%, based on the total unit (100 mol%) of the fluoropolymer, from the viewpoint of the dispersibility of the metal salt in the insulating coating. Is particularly preferred.
  • the fluorine atom content of the fluoropolymer is not particularly limited, but is preferably 15 to 30 wt% (mass%) from the viewpoint of dispersibility of the metal salt in the insulating coating.
  • the fluoropolymer may have “other units” other than the units based on the fluoroolefin.
  • the first embodiment of the “other unit” is a unit other than a unit based on a fluoroolefin, which is a vinyl ether, allyl ether or vinyl carboxylate unit based on the monomer A having an alicyclic alkyl group. Is preferred.
  • the monomer A has a good alternating polymerizability with the fluoroolefin, and the coating film containing the fluoropolymer having the unit has a water vapor transmission rate. It was confirmed that it was low and exhibited particularly excellent physical properties as an insulating coating for electrical steel sheets.
  • the alicyclic alkyl group in the monomer A is preferably an alicyclic alkyl group having 3 to 20 carbon atoms, more preferably 4 to 15 carbon atoms.
  • Specific examples of the monomer A include cyclohexyl vinyl ether, 2-ethylhexyl vinyl ether, cyclohexyl allyl ether, 2-ethylhexyl allyl ether, vinyl cyclohexanecarboxylate, vinyl 2-ethylhexanecarboxylate, and the like.
  • the content of the unit based on the monomer A is preferably 5 to 40 mol% with respect to the total unit (100 mol%) of the fluoropolymer from the viewpoint of forming an insulating film having a low water vapor transmission rate. % Is particularly preferred.
  • a second embodiment of the “other unit” is a unit other than the unit based on the fluoroolefin and the unit based on the monomer A, and is a vinyl ether, allyl ether or vinyl carboxylate, and has a crosslinkable group. Units based on monomer B are preferred. According to the study by the present inventors, when the fluoropolymer in the insulating film is a fluoropolymer having a crosslinked structure, the permeability of water vapor, oxygen and carbon dioxide is low, and An insulating film having excellent adhesion can be obtained.
  • the crosslinkable group is preferably a hydroxy group, a carboxy group, an amino group or a hydrolyzable silyl group, and particularly preferably a hydroxy group.
  • monomers B having a crosslinkable group specific examples include hydroxyalkyl vinyl ether, hydroxyalkyl vinyl ester, hydroxyalkyl allyl ether, hydroxyalkyl allyl ester, hydroxyalkyl ester of acrylic acid, Examples include methacrylic acid hydroxyalkyl esters (the hydroxyalkyl group in these monomers may be a chain or a ring).
  • 2-hydroxyethyl vinyl ether 4-hydroxybutyl vinyl ether, cyclohexanedimethanol monovinyl ether, hydroxyethyl allyl ether, hydroxyethyl acrylate, hydroxyethyl methacrylate, represented by the formula: X′-Y′-OH And a monomer represented by the formula: X′-Z′-OH.
  • X′—Y′—OH and X′—Z′—OHX ′ are vinyl group, vinyl ether group, allyl group, allyl ether group, propenyl group, isopropenyl group, acryloyl group or methacryloyl group
  • Y ′ Is an n-nonylene group or cyclohexane-1,4-dimethylene group
  • Z ′ is a group represented by the formula —C a H 2a — (OC b H 2b ) c — (a is an integer of 1 to 10)
  • B is an integer from 1 to 4
  • c is an integer from 2 to 20, and so on.
  • monomer B for example, a monomer of the formula: X′-Y′-OH and a monomer of the formula: X′-Z′-OH
  • monomer B include the following compounds (provided that In the following formulae, -cycloC 6 H 10 -represents a 1,4-cyclohexylene group).
  • the content of the units based on the monomer B is preferably 5 to 20 mol% with respect to the total units (100 mol%) of the fluoropolymer.
  • the crosslinkable group derived from the monomer B may react with other components in the insulating coating.
  • the crosslinkable group may react with a crosslinker having two or more groups that react with the crosslinkable group to form a crosslinked structure in the insulating coating. That is, in the insulating coating, the fluoropolymer may have a crosslinked structure.
  • the third aspect of “other units” includes units other than units based on fluoroolefin, units based on monomer A and units based on monomer B.
  • the monomer forming the unit include nonyl vinyl ether, 2-ethylhexyl vinyl ether, hexyl vinyl ether, ethyl vinyl ether, n-butyl vinyl ether, alkyl vinyl ethers such as tert-butyl vinyl ether, ethyl allyl ether, hexyl allyl ether, etc.
  • the fluoropolymer in the present invention include a unit based on a fluoroolefin, a unit based on the monomer A, and a unit based on the monomer B, and all units (100 mol%) of the fluoropolymer.
  • a fluorine-containing polymer having a crosslinked structure.
  • the metal salt is not particularly limited as long as it is a component that improves the antirust property of the electrical steel sheet with an insulating coating, and phosphoric acid, nitric acid, carbonic acid, sulfuric acid, hexafluorosilicic acid, hexafluorotitanic acid, and hexafluorozirconic acid.
  • a metal salt of at least one inorganic acid selected from: or a metal salt of at least one organic acid selected from formic acid, acetic acid, oxalic acid, lactic acid, malonic acid, and tartaric acid is preferable.
  • the inorganic acid is preferably phosphoric acid from the viewpoint of rust prevention of the electrical steel sheet with an insulating coating.
  • the metal of the metal salt is preferably Li, Al, Mg, Ca, Sr, Ti, Ni, Mn, Co, Zr, Fe, Cu or Ag, and Al is particularly preferable from the viewpoint of rust prevention of the electrical steel sheet with an insulating coating.
  • the metal salt is preferably a reducible metal salt capable of reducing an oxidizing component (usually moisture, oxygen and carbon dioxide in the atmosphere) that can corrode the electrical steel sheet, and the reduction forms a sacrificial layer on the surface of the electrical steel sheet.
  • a reducing metal salt that can suppress corrosion of the steel sheet is particularly preferred.
  • the insulating coating may contain components other than the above-mentioned fluoropolymer and metal salt, and examples thereof include other components that may be contained in an aqueous surface treatment agent described later.
  • the content of the fluoropolymer in the insulating film is not particularly limited, but is preferably 0.01 to 20.0% by mass and particularly preferably 0.1 to 18.0% by mass with respect to the total mass of the insulating film.
  • the content of the metal salt in the insulating coating is not particularly limited, but is preferably 1 to 1000 parts by mass, particularly preferably 10 to 700 parts by mass with respect to 100 parts by mass of the fluoropolymer. If the content of the metal salt is not less than the lower limit of the above range, the electrical steel sheet with an insulating coating is excellent in rust prevention, and if it is not more than the upper limit of the above range, the appearance of the insulating coating is excellent.
  • Adhesion amount of the insulating coating is not particularly limited, as coating weight per one surface of the electromagnetic steel sheet is preferably 0.1 ⁇ 1000g / m 2, particularly preferably 0.5 ⁇ 500g / m 2.
  • the manufacturing method of an insulating film is not specifically limited, A well-known method is employable.
  • the following method using an aqueous surface treating agent is preferable.
  • the method using an aqueous surface treating agent will be described in detail.
  • the water-based surface treatment agent is a surface treatment agent containing water and used for forming an insulating film on the surface of an electrical steel sheet, and is a unit based on fluoroolefin, vinyl ether, allyl ether or vinyl carboxylate, A unit based on monomer A having a cyclic alkyl group, and a monomer having vinyl ether, allyl ether or vinyl carboxylate and having at least one crosslinkable group selected from a hydroxyl group, a carboxy group and an amino group
  • a fluorine-containing polymer having units based on B, a crosslinking agent, and a metal salt are included.
  • Respective units constituting the fluorinated polymer in the aqueous surface treating agent (units based on fluoroolefin, units based on monomer A which is vinyl ether, allyl ether or vinyl carboxylate and has an alicyclic alkyl group, and , Vinyl ether, allyl ether, or vinyl carboxylate, a unit based on monomer B having at least one crosslinkable group selected from a hydroxyl group, a carboxy group, and an amino group) and preferred embodiments thereof, and respective units
  • the preferable range of the content with respect to all the units (100 mol%) of the fluoropolymer is as described for the fluoropolymer contained in the insulating coating described above.
  • the hydroxyl value of the fluorine-containing polymer is preferably 20 mgKOH / g or more, particularly preferably 40 mgKOH / g or more. In this case, if the hydroxyl value of the fluorinated polymer is not less than the above lower limit, the solvent resistance of the insulating coating is remarkably improved by the reaction with the crosslinking agent. Although the said hydroxyl value is not specifically limited, 200 mgKOH / g or less is preferable.
  • metal salts contained in the aqueous surface treatment agent and preferred embodiments thereof are also as described for the metal salts contained in the above-mentioned insulating coating.
  • the crosslinking agent contained in the aqueous surface treatment agent is not particularly limited as long as it is a compound that has two or more groups capable of reacting with the crosslinkable group of the fluoropolymer and crosslinks the fluoropolymer.
  • a crosslinking agent is suitably selected according to the kind of unit which has a crosslinkable group in a fluoropolymer. For example, when the crosslinkable group contained in the fluoropolymer is a hydroxy group, a compound having two or more isocyanate groups is preferred. When the crosslinkable group contained in the fluoropolymer is an amino group, A compound having two or more isocyanate groups is preferred.
  • the crosslinkable group contained in the fluoropolymer is a carboxy group
  • a compound having two or more amino groups is preferred.
  • a known isocyanate curing agent, a known blocked isocyanate curing agent, or the like can be used.
  • a well-known amino resin can be used as a compound which has 2 or more of amino groups.
  • the crosslinking agent may be a curing agent having self-crosslinking properties.
  • the solid content concentration of the fluoropolymer is preferably 0.1 to 50.0% by mass, and particularly preferably 0.2 to 40.0% by mass. If solid content concentration is more than the lower limit of the said range, the slipperiness after strain relief annealing will be excellent. If solid content concentration is below the upper limit of the said range, the adhesiveness to the electrical steel sheet of an insulating film will be excellent.
  • the aqueous surface treatment agent contains a polymer other than the fluorine-containing polymer (for example, acrylic resin), the fluorine-containing polymer in the aqueous surface treatment agent and the polymer other than the fluorine-containing polymer.
  • the total solid content concentration is preferably within the above-described range.
  • the water-based surface treatment agent preferably contains 1 to 1000 parts by mass of metal salt, particularly preferably 10 to 700 parts by mass, per 100 parts by mass of the fluoropolymer. If the content of the metal salt is not less than the lower limit of the above range, the electrical steel sheet with an insulating coating is excellent in rust prevention, and if it is not more than the upper limit of the above range, the appearance characteristics of the insulating coating are excellent.
  • the content of the crosslinking agent is preferably 0.1 to 50.0 parts by mass, particularly preferably 0.5 to 30.0 parts by mass with respect to 100 parts by mass of the fluoropolymer. If the content of the crosslinking agent is not less than the lower limit of the above range, the water resistance of the insulating coating is excellent, and if it is not more than the upper limit of the above range, the adhesion between the insulating coating and the electrical steel sheet is excellent.
  • the aqueous surface treatment agent may contain other components other than the fluoropolymer, the crosslinking agent, and the metal salt as necessary.
  • Other components include organic solvents, polymers other than fluoropolymers, emulsifiers, inorganic coloring pigments, organic coloring pigments, extender pigments, curing catalysts, plasticizers, preservatives, antifungal agents, antifoaming agents, Examples include leveling agents, pigment dispersants, anti-settling agents, anti-sagging agents, matting agents, UV absorbers, antioxidants, film-forming aids, and thickeners.
  • the aqueous surface treatment agent contains a film-forming aid
  • an insulating coating excellent in physical properties such as coating appearance, water resistance, adhesion to electrical steel sheets, and rust prevention can be obtained.
  • film-forming aids include dipropylene glycol mono n-butyl ether, diethylene glycol monoethyl ether acetate, 2,2,4-trimethyl-1,3 pentadiol mono (2-methylpropionate), diethylone glycol diethyl Examples include ether.
  • organic solvent examples include alcohol (methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, secondary butanol, tertiary butanol, pentanol, etc.), cellosolve (methyl cellosolve, ethyl cellosolve, Isopropyl cellosolve, butyl cellosolve, secondary butyl cellosolve, etc.), propylene glycol derivatives (propylene glycol methyl ether, dipropylene glycol methyl ether, propylene glycol methyl ether acetate etc.), ethylene glycol ethyl ether acetate, ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone) Etc.) and aromatic hydrocarbons (toluene, xylene, etc.).
  • alcohol methanol, ethanol, n-propanol, isopropanol
  • the electrical steel sheet with an insulating coating is heated (baked) as necessary after the aqueous surface treatment agent is brought into contact with the surface of the electrical steel sheet by means such as a coating method using a roll coater, a spray method, or a dip method. ) It is preferable to manufacture by processing.
  • the fluoropolymer and the crosslinking agent react to form a crosslinked structure in the insulating coating.
  • the heating temperature is, for example, 150 to 400 ° C.
  • the heating time is, for example, 15 to 120 seconds.
  • the above-mentioned electrical steel sheet with an insulating coating is excellent in water resistance and rust prevention under a high temperature and humidity environment, is excellent in adhesion of the insulating coating to the electrical steel sheet, and is excellent in the appearance characteristics of the insulating coating.
  • the electrical steel sheet with an insulating coating of the present invention can be preferably applied to a motor (specifically, a stator and a rotor of a motor), an EI core of a transformer, etc., and a motor is preferable.
  • the electrical steel sheet with an insulating coating of the present invention comprises a power plant generator, an ultra-high voltage substation and a primary and secondary substation transformer, a factory power motor and transformer, a train-related train.
  • Motors and cooling motors building transformers, air conditioners, air conditioning motors, road lighting ballasts, fluorescent light ballasts (a type of transformer), motors for washing machines and dehydrators, floppy disks in floppy disk drives It can be used as a stepping motor that rotates the head and a stepping motor that moves the head, a motor for a shave shaver, a compressor motor for a refrigerator and an air conditioner, a power supply transformer for a TV, and an iron core for a hybrid car motor.
  • EVE ethyl vinyl ether
  • CHVE cyclohexyl vinyl ether
  • CHMVE: CH 2 CHOCH 2 -cycloC 6 H 10 -CH 2 OH
  • CTFE chlorotrifluoroethylene
  • 4-HBVE 4-hydroxybutyl vinyl ether
  • 2-EHVE 2-ethylhexyl vinyl ether
  • PVDF polyvinylidene fluoride
  • aqueous liquid (1) containing the fluoropolymer (1) was prepared as follows. In a stainless steel autoclave with a stirrer having an internal volume of 2500 mL, water (1280 g), EVE (185 g), CHVE (244 g), CM-EOVE (47 g), CHMVE (194 g), ion-exchanged water (1280 g), potassium carbonate ( 2.0 g), ammonium persulfate (1.3 g), nonionic emulsifier (manufactured by Nippon Emulsifier, Newcol (registered trademark) -2320) (33 g), and anionic emulsifier (sodium lauryl sulfate) (1.4 g) Then, the autoclave was cooled with ice and depressurized with nitrogen gas so that the inside of the autoclave became 0.4 MPaG.
  • the ratio of each unit in the fluoropolymer (1) can be determined by analysis with 1 H-NMR or 13 C-NMR.
  • the fluorine atom content of the fluoropolymer (1) was measured by the following procedure.
  • the fluoropolymer (1) was recovered from the aqueous liquid (1) by centrifugation. 2) After coating with fluoropolymer (1) and potassium carbonate, it was thermally decomposed at 600 ° C. for 1 hour in a crucible. 3) The fluoride ion intensity of an aqueous solution in which the produced potassium fluoride was dissolved in water was measured by an ion electrode method. 4) The fluorine atom content of the fluoropolymer (1) was calculated from the measured fluoride ion intensity and the calibration value of the polytetrafluoroethylene homopolymer having a known fluorine concentration.
  • MEK methyl ethyl ketone
  • the proportion neutralized with triethylamine was 70 mol%.
  • the ratio of each unit in the fluoropolymer (2) was determined by analysis with 1 H-NMR or 13 C-NMR, and the ratio of the fluoropolymer (2) determined in the same manner as in Preparation Example 1 was used.
  • the fluorine atom content was 25.6% by mass.
  • aqueous liquid (3) containing the fluoropolymer (3) was prepared as follows.
  • the ratio of each unit in the fluoropolymer (3) was determined by analysis with 1 H-NMR or 13 C-NMR, and the ratio of the fluoropolymer (3) determined in the same manner as in Preparation Example 1 was used.
  • the fluorine atom content was 22.2% by mass.
  • Example 1 Aluminum phosphate (10.0 g), aqueous liquid (1) (5.0 g) of the fluoropolymer (1) obtained in Preparation Example 1, dipropylene glycol mono n-butyl ether (0. 4 g), thickener (Akzo Nobel, Vermodor (registered trademark) 2150) (0.01 g), water-dispersed isocyanate curing agent (Sumika Bayer, Bihydur (registered trademark) 3100) (0. 6 g) and ion-exchanged water (83.99 g) were mixed to prepare an aqueous surface treating agent (1).
  • the solid content concentration of the fluoropolymer (1) in the aqueous surface treating agent (1) was 2.5% by mass.
  • the obtained water-based surface treatment agent (1) is rolled on both sides of a 0.5 mm thick magnetic steel sheet so that the amount of insulation coating (the amount of adhesion per side) after baking is 1.0 g / m 2.
  • an insulating coating containing a fluoropolymer having a crosslinked structure was formed on both surfaces of the electrical steel sheet by heating for 30 seconds so that the maximum temperature reached 270 ° C. in a hot air oven.
  • the water vapor transmission rate per 1 ⁇ m film thickness, the oxygen transmission rate per 1 ⁇ m film thickness, and the carbon dioxide transmission rate per 1 ⁇ m film thickness of the separately prepared fluoropolymer (1) sheet were 1. They were 8 g / m 2 ⁇ day, 0.02 mol / m 2 ⁇ s ⁇ Pa, and 0.02 mol / m 2 ⁇ s ⁇ Pa.
  • the fluoropolymer (1) and a water-dispersed isocyanate curing agent manufactured by Sumika Bayer, Vihijoule (registered trademark) 3100 were used. .
  • the sheet of the fluoropolymer (1) contained a cross-linked structure.
  • the usage ratio of the fluoropolymer (1) to the water-dispersed isocyanate curing agent was the same as the usage ratio in the aqueous surface treatment agent (1).
  • Example 2 The aqueous surface treatment agent (2) was changed in the same manner as in Example 1 except that the aqueous liquid (1) was changed to the aqueous liquid (2) and the solid content concentration of the fluoropolymer (2) was 2.5% by mass. And an insulating coating containing a fluoropolymer having a crosslinked structure was formed on both surfaces of the electrical steel sheet.
  • the water vapor transmission rate per 1 ⁇ m film thickness, the oxygen transmission rate per 1 ⁇ m film thickness, and the carbon dioxide transmission rate per 1 ⁇ m film thickness of the separately prepared fluoropolymer (2) sheet were 1. They were 9 g / m 2 ⁇ day, 0.03 mol / m 2 ⁇ s ⁇ Pa, and 0.03 mol / m 2 ⁇ s ⁇ Pa.
  • the fluoropolymer (2) and a water-dispersed isocyanate curing agent manufactured by Sumika Bayer, Vihijoule (registered trademark) 3100 were used. .
  • the sheet of the fluoropolymer (2) contained a cross-linked structure.
  • the use amount ratio between the fluoropolymer (2) and the water-dispersed isocyanate curing agent was the same as the use amount ratio in the aqueous surface treatment agent (2).
  • a water-based surface treatment agent (3) having a solid content concentration (total concentration of PVDF and acrylic resin) of 2.5% by mass was prepared in the same manner as in Example 1 except that the amount was changed to 0.0 mol%. Using this, an insulating coating containing PVDF and acrylic resin was formed on both surfaces of the electrical steel sheet.
  • the separately prepared PVDF sheet (sheet made of PVDF) had a water vapor transmission rate per 1 ⁇ m film thickness, an oxygen transmission rate per 1 ⁇ m film thickness, and a carbon dioxide transmission rate per 1 ⁇ m film thickness of 19.6 g. / M 2 ⁇ day, 0.5 mol / m 2 ⁇ s ⁇ Pa, and 0.6 mol / m 2 ⁇ s ⁇ Pa.
  • aqueous surface treating agent (4) was prepared in the same manner as in Example 1 except that the aqueous liquid (1) was changed to the aqueous liquid (3) and no water-dispersed isocyanate curing agent was added. Using this, an insulating coating containing a fluoropolymer having no cross-linked structure was formed on both surfaces of the electrical steel sheet.
  • the water vapor transmission rate per film thickness of 1 ⁇ m, the oxygen transmission rate per film thickness of 1 ⁇ m, and the film thickness of 1 ⁇ m of the separately prepared fluoropolymer (3) sheet (sheet made of the fluoropolymer (3)).
  • the permeate carbon dioxide permeability was 1.0 g / m 2 ⁇ day, 0.2 mol / m 2 ⁇ s ⁇ Pa, and 0.1 mol / m 2 ⁇ s ⁇ Pa, respectively.
  • Table 1 shows the physical properties of the fluoropolymer contained in each insulating film, and Table 2 shows the evaluation results.
  • Adhesiveness A test piece of a magnetic steel sheet with an insulation coating having a length of 50 mm and a width of 25 mm was wound around a steel bar having a diameter of 5 mm, and a tape peeling test was performed on the wound outer part (insulation coating) to remain on the magnetic steel sheet. The state of the insulating coating was visually evaluated. ⁇ is a pass. ⁇ : No film peeling ⁇ : Film peeling occurred
  • the “crosslinked structure” column represents the presence or absence of a crosslinked structure of the fluoropolymer in the insulating coating.
  • water vapor transmission rate”, “oxygen transmission rate”, and “carbon dioxide transmission rate” represent measured values of the fluoropolymer sheets prepared in each Example and each Comparative Example.
  • the electrical steel sheet with an insulating coating of the present invention can be applied to various uses, for example, power plant generators, ultra-high voltage substations and primary, secondary substation transformers, factory power motors and transformers, trains, etc.
  • train motors and air conditioning motors building transformers, air conditioners, air conditioning motors, road lighting ballasts, fluorescent light ballasts (a type of transformer), washing machine and dehydrator motors, floppy (registered) (Trademark) Motor for rotating floppy (registered trademark) in disk drive and stepping motor for moving head, motor for shave shaver, compressor motor for refrigerator and air conditioner, power transformer for TV, and iron core for hybrid car motor Can be used for etc.

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Abstract

L'invention concerne : une tôle d'acier électromagnétique dotée d'un revêtement isolant qui présente une excellente résistance à l'eau et des propriétés de prévention de la rouille dans des environnements humides à haute température, une excellente adhésivité à des tôles d'acier électromagnétiques, et d'excellentes caractéristiques d'aspect ; et un agent de traitement de surface aqueux utilisé pour former ladite tôle d'acier électromagnétique. Une tôle d'acier électromagnétique dotée d'un revêtement isolant qui comprend une tôle d'acier électromagnétique et un revêtement isolant disposé sur la tôle d'acier électromagnétique et comprenant un polymère fluoré à motifs basés sur une fluorooléfine, et un sel métallique, est caractérisée en ce que le polymère fluoré satisfait aux conditions 1 et 2. Condition 1 : Lorsque le polymère fluoré prend la forme d'une feuille, la perméabilité à la vapeur d'eau par 1 µm d'épaisseur de la feuille de polymère fluoré est de 0,01 à 5 g/m2∙jour. Condition 2 : Lorsque le polymère fluoré prend la forme d'une feuille, la perméabilité à l'oxygène par 1 µm d'épaisseur de la feuille de polymère fluoré est inférieure à 0,2 mol/m2∙s∙Pa.
PCT/JP2016/062276 2015-04-20 2016-04-18 Tôle d'acier électromagnétique à revêtement isolant et agent de traitement de surface aqueux WO2016171104A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023054222A1 (fr) * 2021-09-30 2023-04-06 富士フイルム株式会社 Composition, produit durci, procédé de production d'un produit durci, structure et dispositif
WO2023145800A1 (fr) * 2022-01-26 2023-08-03 日本製鉄株式会社 Tôle d'acier électromagnétique non orientée

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003012826A (ja) * 2001-06-29 2003-01-15 Nippon Steel Corp 鋼材被覆用フィルム及び樹脂被覆鋼材
WO2012057168A1 (fr) * 2010-10-29 2012-05-03 新日本製鐵株式会社 Feuille d'acier électromagnétique et procédé pour sa production
WO2013153020A2 (fr) * 2012-04-12 2013-10-17 Nuovo Pignone Srl Procédé permettant d'empêcher la corrosion et composant obtenu au moyen d'un tel procédé

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003012826A (ja) * 2001-06-29 2003-01-15 Nippon Steel Corp 鋼材被覆用フィルム及び樹脂被覆鋼材
WO2012057168A1 (fr) * 2010-10-29 2012-05-03 新日本製鐵株式会社 Feuille d'acier électromagnétique et procédé pour sa production
WO2013153020A2 (fr) * 2012-04-12 2013-10-17 Nuovo Pignone Srl Procédé permettant d'empêcher la corrosion et composant obtenu au moyen d'un tel procédé

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023054222A1 (fr) * 2021-09-30 2023-04-06 富士フイルム株式会社 Composition, produit durci, procédé de production d'un produit durci, structure et dispositif
WO2023145800A1 (fr) * 2022-01-26 2023-08-03 日本製鉄株式会社 Tôle d'acier électromagnétique non orientée

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