WO2016171104A1 - Electromagnetic steel sheet with insulating coating and aqueous surface treatment agent - Google Patents

Electromagnetic steel sheet with insulating coating and aqueous surface treatment agent Download PDF

Info

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
Authority
WO
WIPO (PCT)
Prior art keywords
fluoropolymer
steel sheet
insulating coating
sheet
electrical steel
Prior art date
Application number
PCT/JP2016/062276
Other languages
French (fr)
Japanese (ja)
Inventor
俊 齋藤
将崇 相川
Original Assignee
旭硝子株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 旭硝子株式会社 filed Critical 旭硝子株式会社
Priority to JP2017514114A priority Critical patent/JP6733665B2/en
Publication of WO2016171104A1 publication Critical patent/WO2016171104A1/en

Links

Classifications

    • 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.

Abstract

Provided are: an electromagnetic steel sheet with an insulating coating that has excellent water resistance and rust preventing properties in high temperature, humid environments, excellent adhesiveness to electromagnetic steel sheets, and excellent appearance characteristics; and an aqueous surface treatment agent used for forming said electromagnetic steel sheet. An electromagnetic steel sheet with an insulating coating that comprises an electromagnetic steel sheet, and an insulating coating disposed on the electromagnetic steel sheet and comprising a fluorine-containing polymer with units based on a fluoroolefin, and a metal salt, is characterized in that the fluorine-containing polymer satisfies conditions 1 and 2. Condition 1: When the fluorine-containing polymer is made into a sheet, the water vapor permeability per 1 µm thickness of the fluorine-containing polymer sheet is 0.01-5 g/m2∙day. Condition 2: When the fluorine-containing polymer is made into a sheet, the oxygen permeability per 1 µm thickness of the fluorine-containing polymer sheet is less than 0.2 mol/m2∙s∙Pa.

Description

絶縁被膜付き電磁鋼板および水系表面処理剤Electrical steel sheet with insulation coating and water-based surface treatment agent
　本発明は、高温湿潤環境下での耐水性および防錆性に優れ、絶縁被膜の密着性、被膜外観にも優れた絶縁被膜付き電磁鋼板、該絶縁被膜付き電磁鋼板を有するモーター、および電磁鋼板の表面に絶縁被膜を形成するために用いられる水系表面処理剤に関する。 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.
　モーターやトランス等の鉄芯に使用される電磁鋼板は、大気中の水分および酸素によって酸化されて腐食すると、金属強度や電磁性能が低下する。そのため、酸化により腐食しにくい電磁鋼板として、表面にクロメート被膜を有する電磁鋼板が使用されている。クロメート被膜としては、反応型クロメート処理法（クロム酸クロメート、リン酸クロメート等のクロムを含む表面処理剤を用いる方法）や、塗布型クロメート処理法（クロム酸塩またはクロム酸塩とシリカを含む表面処理剤を用いる方法）によって形成された被膜が挙げられる。 When electrical steel sheets used for iron cores such as motors and transformers are oxidized and corroded by moisture and oxygen in the atmosphere, the metal strength and electromagnetic performance are reduced. Therefore, 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. Examples of 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).
　一方、近年では、電磁鋼板の渦電流損失を低減するために、その表面に電気絶縁性の被膜を有する電磁鋼板も提案されている。かかる電磁鋼板として、含フッ素重合体を含む絶縁被膜を表面に有する絶縁被膜付き電磁鋼板が提案されている（特許文献１および２参照。）。 On the other hand, recently, in order to reduce the eddy current loss of the electrical steel sheet, an electrical steel sheet having an electrically insulating coating on its surface has also been proposed. As such an electrical steel sheet, 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).
特開２００２－３０９３７９号公報JP 2002-309379 A 国際公開第２０１２／０５７１６８号パンフレットInternational Publication No. 2012/057168 Pamphlet
　しかし、特許文献１に記載の絶縁被膜は電磁鋼板との密着性が低く剥離し易く、結果として、高温湿潤環境下において絶縁被膜付き電磁鋼板の防錆性が劣る問題があった。
　また、特許文献２に記載の絶縁被膜は耐水性が低く、特に、高温湿潤環境下において絶縁被膜付き電磁鋼板の防錆性が劣る問題があった。
　さらに、絶縁被膜に関しては、その外観特性も優れることが求められる。 However, 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.
In addition, 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.
　本発明の課題は、高温湿潤環境下での耐水性および防錆性に優れ、絶縁被膜の電磁鋼板への密着性に優れ、かつ、絶縁被膜の外観特性にも優れた絶縁被膜付き電磁鋼板を提供することである。
　また、本発明の他の課題は、上記諸特性に優れた絶縁被膜付き電磁鋼板を有するモーター、および、かかる絶縁被膜を形成するために用いられる水系表面処理剤を提供することである。 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.
　本発明は、以下の要旨を有する。
（１）電磁鋼板と、上記電磁鋼板上に配置された、フルオロオレフィンに基づく単位を有する含フッ素重合体および金属塩を含む絶縁被膜を有する絶縁被膜付き電磁鋼板であって、含フッ素重合体が、以下の要件１および要件２を満たすことを特徴とする絶縁被膜付き電磁鋼板。
　要件１：上記含フッ素重合体をシート状とした際、含フッ素重合体シートの膜厚１μｍあたりの水蒸気透過率が０．０１～５ｇ／ｍ２・ｄａｙである。
　要件２：上記含フッ素重合体をシート状とした際、含フッ素重合体シートの膜厚１μｍあたりの酸素透過率が０．２ｍｏｌ／ｍ２・ｓ・Ｐａ未満である。
（２）上記含フッ素重合体が、さらに、以下の要件３を満たす、（１）に記載の絶縁被膜付き電磁鋼板。
　要件３：上記含フッ素重合体をシート状とした際、含フッ素重合体シートの膜厚１μｍあたりの二酸化炭素透過率が０．１ｍｏｌ／ｍ２・ｓ・Ｐａ未満である。
（３）上記含フッ素重合体のフッ素原子含有量が、１５～３０ｗｔ％である、（１）または（２）に記載の絶縁被膜付き電磁鋼板。
（４）上記含フッ素重合体が、ビニルエーテル、アリルエーテルまたはカルボン酸ビニルであって、脂環式アルキル基を有する単量体Ａに基づく単位を有する、（１）～（３）のいずれかに記載の絶縁被膜付き電磁鋼板。
（５）上記単量体Ａに基づく単位の含有量が、上記含フッ素重合体の全（１００ｍｏｌ％）に対して、５～４０ｍｏｌ％である、（４）に記載の絶縁被膜付き電磁鋼板。
（６）上記含フッ素重合体が、ビニルエーテル、アリルエーテルまたはカルボン酸ビニルであって、水酸基、カルボキシ基およびアミノ基から選ばれる少なくとも１種の架橋性基を有する単量体Ｂに基づく単位を有する、（１）～（５）のいずれかに記載の絶縁被膜付き電磁鋼板。
（７）上記単量体Ｂに基づく単位の含有量が、上記含フッ素重合体の全（１００ｍｏｌ％）に対して、５～２０ｍｏｌ％である、（６）に記載の絶縁被膜付き電磁鋼板。
（８）上記含フッ素重合体が、架橋構造を有する、（１）～（７）のいずれかに記載の絶縁被膜付き電磁鋼板。
（９）（１）～（８）のいずれかに記載の絶縁被膜付き電磁鋼板を有するモーター。
（１０）電磁鋼板の表面に絶縁被膜を形成するために用いられる、水を含む水系表面処理剤であって、
　フルオロオレフィンに基づく、ビニルエーテル、アリルエーテルまたはカルボン酸ビニルであって、脂環式アルキル基を有する単量体Ａに基づく、並びに、ビニルエーテル、アリルエーテルまたはカルボン酸ビニルであって、水酸基、カルボキシ基およびアミノ基から選ばれる少なくとも１種の架橋性基を有する単量体Ｂに基づく単位を有する含フッ素重合体と、架橋剤と、金属塩と、を含むことを特徴とする水系表面処理剤。
（１１）上記架橋剤が、イソシアネート基またはアミノ基を２個以上有する化合物である、（１０）に記載の水系表面処理剤。
（１２）上記金属塩が、リン酸、硝酸、炭酸、硫酸、ヘキサフルオロケイ酸、ヘキサフルオロチタン酸、およびヘキサフルオロジルコン酸から選ばれる少なくとも１種の無機酸の金属塩、または、蟻酸、酢酸、シュウ酸、乳酸、マロン酸、および酒石酸から選ばれる少なくとも１種の有機酸の金属塩である、（１０）または（１１）に記載の水系表面処理剤。
（１３）前記金属塩の金属が、Ｌｉ、Ａｌ、Ｍｇ、Ｃａ、Ｓｒ、Ｔｉ、Ｎｉ、Ｍｎ、Ｃｏ、Ｚｒ、Ｆｅ、ＣｕまたはＡｇである、（１０）～（１２）のいずれか１項に記載の水系表面処理剤。 The present invention has the following gist.
(1) 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 μm 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 μm 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 μm of film thickness of the fluoropolymer sheet is less than 0.1 mol / m 2 · s · Pa.
(3) The electrical steel sheet with an insulating coating according to (1) or (2), wherein the fluorine-containing content of the fluoropolymer is 15 to 30 wt%.
(4) 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.
(5) The electrical steel sheet with an insulating coating according to (4), wherein the content of the units based on the monomer A is 5 to 40 mol% with respect to the total (100 mol%) of the fluoropolymer.
(6) 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 electrical steel sheet with an insulating coating according to any one of (1) to (5).
(7) The electrical steel sheet with an insulating coating according to (6), wherein the content of the unit based on the monomer B is 5 to 20 mol% with respect to the total (100 mol%) of the fluoropolymer.
(8) The electrical steel sheet with an insulating coating according to any one of (1) to (7), wherein the fluoropolymer has a crosslinked structure.
(9) A motor having the electromagnetic steel sheet with an insulating coating according to any one of (1) to (8).
(10) A water-based surface treatment agent containing water, used to form an insulating coating on the surface of an electromagnetic steel sheet,
Based on fluoroolefin, vinyl ether, allyl ether or vinyl carboxylate, based on monomer A having an alicyclic alkyl group, and vinyl ether, allyl ether or vinyl carboxylate, having a hydroxyl group, a carboxy group and An aqueous surface treating agent comprising a fluoropolymer having a unit based on the monomer B having at least one crosslinkable group selected from amino groups, a crosslinking agent, and a metal salt.
(11) The aqueous surface treating agent according to (10), wherein the crosslinking agent is a compound having two or more isocyanate groups or amino groups.
(12) 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 The aqueous surface treating agent according to (10) or (11), which is a metal salt of at least one organic acid selected from oxalic acid, lactic acid, malonic acid, and tartaric acid.
(13) 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. A water-based surface treatment agent described in 1.
　本発明によれば、高温湿潤環境下での耐水性および防錆性に優れ、絶縁被膜の電磁鋼板への密着性に優れ、かつ、絶縁被膜の外観特性にも優れる絶縁被膜付き電磁鋼板が提供される。
　また、本発明によれば、上記優れた諸特性を有する絶縁被膜付き電磁鋼板を有するモーター、および、電磁鋼板の表面にかかる絶縁被膜を容易に形成できる水系表面処理剤が提供される。 According to the present invention, there is provided 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.
Moreover, according to this invention, 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.
　以下の用語の定義は、本明細書および特許請求の範囲にわたって適用される。
　重合体を構成する「単位」とは、重合体中に存在して重合体を構成する、単量体に由来する部分を意味する。炭素－炭素不飽和二重結合を有する単量体の付加重合により生じる、該単量体に由来する単位は、該不飽和二重結合が開裂して生じた２価の単位である。また、ある単位の構造を重合体形成後に化学的に変換したものも単位という。なお、以下、場合により、個々の単量体に由来する単位をその単量体名に「単位」を付した名称で呼ぶ。
　「～」を用いて表される数値範囲は、「～」の前後に記載される数値を下限値および上限値として含む範囲を意味する。 The following definitions of terms apply throughout this specification and the claims.
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. Moreover, what unitally converted the structure of a unit after polymer formation is also called a unit. Hereinafter, in some cases, 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.
＜電磁鋼板＞
　絶縁被膜付き電磁鋼板に含まれる電磁鋼板の種類は特に限定されず、公知の電磁鋼板を使用できる。たとえば、電磁鋼板の磁性は、方向性、無方向性、または２方向性のいずれであってもよい。また、１方向性電磁鋼板であれば、その表面にフォルステライト被膜や、張力を発生させるリン酸塩系被膜が存在していてもよい。
　電磁鋼板の化学組成も特に限定されず、方向性電磁鋼板であれば、たとえば、Ｓｉ：２～４質量％、Ｍｎ：≦０．４質量％、Ａｌ：≦０．１質量％の化学組成が挙げられ、無方向性電磁鋼板であれば、たとえば、Ｓｉ：≦４質量％、Ｍｎ：≦１．０質量％、Ａｌ：≦３．０質量％の化学組成が挙げられる。
　電磁鋼板の板厚も、特に限定されず、たとえば、０．０５～１．０ｍｍ程度である。 <Electromagnetic steel sheet>
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. For example, the magnetism of the electrical steel sheet may be any of directionality, non-direction, or bidirectional. In the case of a unidirectional electrical steel sheet, 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%. If it is a non-oriented electrical steel sheet, the chemical composition of Si: <= 4 mass%, Mn: <= 1.0 mass%, Al: <= 3.0 mass% will be mentioned, for example.
The thickness of the electromagnetic steel sheet is not particularly limited, and is, for example, about 0.05 to 1.0 mm.
＜絶縁被膜＞
　絶縁被膜付き電磁鋼板が有する絶縁被膜は、電磁鋼板上に配置されるシート状（膜状）の層である。絶縁被膜の厚みは、通常０．３～３．０μｍが好ましく、０．５～１．５μｍがより好ましい。
　絶縁被膜は、フルオロオレフィンに基づく単位を有する含フッ素重合体および金属塩を含む被膜である。以下、絶縁被膜に含まれる各成分について詳述する。 <Insulating coating>
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 μm, more preferably from 0.5 to 1.5 μm.
The insulating coating is a coating containing a fluoropolymer having a unit based on fluoroolefin and a metal salt. Hereinafter, each component contained in the insulating coating will be described in detail.
（含フッ素重合体）
　絶縁被膜に含まれる含フッ素重合体は、所定の特性を示す。具体的には、まず、含フッ素重合体は、以下の要件１を満たす。つまり、絶縁被膜には、シート状とした際に所定の水蒸気透過率を示す含フッ素重合体が含まれる。
　要件１：含フッ素重合体をシート状とした際、含フッ素重合体シートの膜厚１μｍあたりの水蒸気透過率が０．０１～５ｇ／ｍ２・ｄａｙである。
　水蒸気透過率は、特に、０．０１～２．５ｇ／ｍ２・ｄａｙが好ましく、０．０１～１．９ｇ／ｍ２・ｄａｙがより好ましい。 (Fluoropolymer)
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 μm 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.
　含フッ素重合体をシート状とする方法は特に限定されず、例えば、含フッ素重合体を含む溶液をシート状（膜状）に塗布し、必要に応じて、溶媒を除去する方法や、含フッ素重合体を溶融させて各種成形方法（例えば、押出し成形）によりシート状（膜状）とする方法等が挙げられる。なお、後述するように、水蒸気透過率を測定するために、含フッ素重合体シートとしては、膜厚６０μｍのシートが作製される。
　また、絶縁被膜中の含フッ素重合体が架橋構造を有する場合、含フッ素重合体シートも架橋構造を有する。つまり、絶縁被膜を形成する際に、架橋性基を有する含フッ素重合体と、架橋剤（例えば、架橋性基と反応する基を２個以上有する架橋剤）とを用いる場合は、架橋性基を有する含フッ素重合体と架橋剤とを用いて作製された含フッ素重合体シートを用いて、水蒸気透過率を測定する。これは、酸素透過率および二酸化炭素透過率を測定するために用いられる含フッ素重合体シートに関しても、上記と同様である。 The method of making the fluoropolymer into a sheet is not particularly limited. For example, 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). As will be described later, in order to measure the water vapor transmission rate, a sheet having a film thickness of 60 μm is prepared as the fluoropolymer sheet.
Moreover, when the fluoropolymer in an insulating film has a crosslinked structure, a fluoropolymer sheet also has a crosslinked structure. That is, when an insulating film is formed, when a fluoropolymer having a crosslinkable group and a crosslinker (for example, a crosslinker having two or more groups that react with the crosslinkable group) are used, 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.
　本明細書において、含フッ素重合体シートの水蒸気透過率とは、ＪＩＳ　Ｚ　０２０８のＢ条件（温度　４０℃±０．５℃、湿度　９０％±２％）に準拠して測定される膜厚６０μｍの含フッ素重合体シートの水蒸気透過率の値を、膜厚１μｍあたりに換算した値、つまり、膜厚６０μｍの含フッ素重合体シートの水蒸気透過率の値を６０で除した値である。 In this specification, the water vapor transmission rate of the fluoropolymer sheet is a film thickness of 60 μm 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 μm thickness, that is, the value obtained by dividing the value of water vapor permeability of the fluoropolymer sheet having a thickness of 60 μm by 60.
　また、含フッ素重合体は、以下の要件２を満たす。つまり、絶縁被膜には、シート状とした際に所定の酸素透過率を示す含フッ素重合体が含まれる。
　要件２：含フッ素重合体をシート状とした際、含フッ素重合体シートの膜厚１μｍあたりの酸素透過率が０．２ｍｏｌ／ｍ２・ｓ・Ｐａ未満である。
　酸素透過率は、特に、０．１ｍｏｌ／ｍ２・ｓ・Ｐａ以下が好ましく、０．０５ｍｏｌ／ｍ２・ｓ・Ｐａ以下がより好ましい。下限は特に限定されず、０．００ｍｏｌ／ｍ２・ｓ・Ｐａ超である。
　含フッ素重合体シートの作製方法および定義は、上述の通りである。 Further, 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 μm 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.
　本明細書において、含フッ素重合体シートの酸素透過率は、ＪＩＳ　Ｋ　７１２６－１に準拠して測定される膜厚６０μｍの含フッ素重合体シートの酸素透過率の値を、膜厚１μｍあたりに換算した値、つまり、膜厚６０μｍの含フッ素重合体シートの酸素透過率の値を６０で除した値である。 In this specification, the oxygen permeability of the fluoropolymer sheet is the oxygen permeability value of a fluoropolymer sheet having a film thickness of 60 μm measured in accordance with JIS K 7126-1 per 1 μm 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 μm by 60.
　絶縁被膜は、電磁鋼板の腐食原因となる水と酸素以外の空気中の酸化成分、たとえば、二酸化炭素を透過させないことが好ましい。そのため、含フッ素重合体は、以下の要件３を満たすことが好ましい。
　要件３：含フッ素重合体をシート状とした際、含フッ素重合体シートの膜厚１μｍあたりの二酸化炭素透過率が０．１ｍｏｌ／ｍ２・ｓ・Ｐａ未満である。
　二酸化炭素透過率は、０．０８ｍｏｌ／ｍ２・ｓ・Ｐａ以下が好ましく、０．０５ｍｏｌ／ｍ２・ｓ・Ｐａ以下がより好ましい。下限は特に限定されず、０．００ｍｏｌ／ｍ２・ｓ・Ｐａ超である。
　含フッ素重合体シートの作製方法および定義は、上述の通りである。 It is preferable that the insulating coating does not allow permeation of oxidizing components in the air other than water and oxygen that cause corrosion of the electrical steel sheet, for example, carbon dioxide. Therefore, 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 μm 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.
　本明細書において、含フッ素重合体シートの二酸化炭素透過率は、ＪＩＳ　Ｋ　７１２６－１に準拠して測定される膜厚６０μｍの含フッ素重合体シートの二酸化炭素透過率の値を、膜厚１μｍあたりに換算した値、つまり、膜厚６０μｍの含フッ素重合体シートの二酸化炭素透過率の値を６０で除した値である。 In the present specification, 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 μm 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 μm by 60.
　以下、含フッ素重合体の好ましい態様に関して、詳細に記載する。
　フルオロオレフィンは、炭化水素系オレフィン（一般式ＣｎＨ２ｎ）の水素原子の１個以上がフッ素原子で置換された化合物である。フルオロオレフィンの炭素数ｎは、２～８が好ましく、２～６がより好ましい。
　フルオロオレフィンにおけるフッ素原子の数は、２以上が好ましく、３～４がより好ましい。
　フルオロオレフィンにおいては、フッ素原子で置換されていない水素原子の１個以上が塩素原子で置換されていてもよい。
　含フッ素重合体中のフルオロオレフィンに基づく単位としては、フッ化ビニリデン、トリフルオロエチレン、クロロトリフルオロエチレン、テトラフルオロエチレン、またはヘキサフルオロプロピレンに基づく単位が好ましく、後述する他の単量体との交互重合性の観点から、クロロトリフルオロエチレンまたはテトラフルオロエチレンが特に好ましい。 Hereinafter, it describes in detail regarding the preferable aspect of a fluoropolymer.
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.
In the fluoroolefin, 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.
　なお、含フッ素重合体は、フルオロオレフィンに基づく単位以外の含フッ素単量体に基づく単位を有していてもよい。該含フッ素単量体の具体例としては、アクリル酸トリフルオロエチル、アクリル酸ペンタフルオロプロビル、アクリル酸ペルフルオロシクロヘキシル、メタクリル酸トリフルオロエチル、メタクリル酸ペンタフルオロプロビル、メタクリル酸ペルフルオロシクロヘキシル等が挙げられる。 In addition, the fluoropolymer may have a unit based on a fluoromonomer other than a unit based on a fluoroolefin. Specific examples of the fluorine-containing monomer include trifluoroethyl acrylate, pentafluoropropyl acrylate, perfluorocyclohexyl acrylate, trifluoroethyl methacrylate, pentafluoropropyl methacrylate, and perfluorocyclohexyl methacrylate. It is done.
　フルオロオレフィンに基づく単量体の含有量は、絶縁被膜における金属塩の分散性の観点から、含フッ素重合体の全単位（１００ｍｏｌ％）に対して、２０～８０ｍｏｌ％が好ましく、３０～７０ｍｏｌ％が特に好ましい。
　また、含フッ素重合体のフッ素原子含有量は特に限定されないが、絶縁被膜における金属塩の分散性の観点から、１５～３０ｗｔ％（質量％）が好ましい。 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.
　含フッ素重合体は、フルオロオレフィンに基づく単位以外の「他の単位」を有していてもよい。
　「他の単位」の第一の態様としては、フルオロオレフィンに基づく単位以外の単位であり、ビニルエーテル、アリルエーテルまたはカルボン酸ビニルであって、脂環式アルキル基を有する単量体Ａに基づく単位が好ましい。本発明者らの検討によれば、該単量体Ａはフルオロオレフィンと良好な交互重合性を有し、かつ、該単位を有する含フッ素重合体を構成成分とする被膜は、水蒸気透過率が低く、電磁鋼板の絶縁被膜として特に優れた物性を示すことが確認された。 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. According to the study by the present inventors, 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.
　該単量体Ａにおける脂環式アルキル基は、炭素数が好ましくは３～２０、より好ましくは４～１５の脂環式アルキル基が好ましい。該単量体Ａの具体例としては、シクロヘキシルビニルエーテル、２－エチルヘキシルビニルエーテル、シクロヘキシルアリルエーテル、２－エチルヘキシルアリルエーテル、シクロヘキサンカルボン酸ビニル、２－エチルヘキサンカルボン酸ビニル等が挙げられる。
　単量体Ａに基づく単位の含有量は、水蒸気透過率の低い絶縁被膜を形成する観点から、含フッ素重合体の全単位（１００ｍｏｌ％）に対して、５～４０ｍｏｌ％が好ましく、１０～４０ｍｏｌ％が特に好ましい。 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.
　「他の単位」の第二の態様としては、フルオロオレフィンに基づく単位と上記単量体Ａに基づく単位以外の単位であり、ビニルエーテル、アリルエーテルまたはカルボン酸ビニルであって、架橋性基を有する単量体Ｂに基づく単位が好ましい。本発明者らの検討によれば、絶縁被膜中の含フッ素重合体が架橋構造を有する含フッ素重合体である場合には、水蒸気、酸素および二酸化炭素の透過率が低く、かつ、電磁鋼板との密着性にも優れた絶縁被膜が得られる。
　架橋性基は、ヒドロキシ基、カルボキシ基、アミノ基または加水分解性シリル基が好ましく、ヒドロキシ基が特に好ましい。 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.
　架橋性基を有する単量体Ｂの内、ヒドロキシ基を有する単量体の具体例としては、ヒドロキシアルキルビニルエーテル、ヒドロキシアルキルビニルエステル、ヒドロキシアルキルアリルエーテル、ヒドロキシアルキルアリルエステル、アクリル酸ヒドロキシアルキルエステル、メタクリル酸ヒドロキシアルキルエステル等が挙げられる（これらの単量体におけるヒドロキシアルキル基は、鎖状であってもよく、環状であってもよい。）。より具体的には、２－ヒドロキシエチルビニルエーテル、４－ヒドロキシブチルビニルエーテル、シクロヘキサンジメタノールモノビニルエーテル、ヒドロキシエチルアリルエーテル、アクリル酸ヒドロキシエチル、メタクリル酸ヒドロキシエチル、式：Ｘ’－Ｙ’－ＯＨで表される単量体、式：Ｘ’－Ｚ’－ＯＨで表される単量体等が挙げられる。
　ただし、Ｘ’－Ｙ’－ＯＨ及びＸ’－Ｚ’－ＯＨＸ’中、ビニル基、ビニルエーテル基、アリル基、アリルエーテル基、プロペニル基、イソプロペニル基、アクリロイル基またはメタクリロイル基であり、Ｙ’はｎ－ノニレン基またはシクロヘキサン－１，４－ジメチレン基であり、Ｚ’は式－ＣａＨ２ａ－（ＯＣｂＨ２ｂ）ｃ－で表される基（ａは１～１０の整数であり、ｂは１～４の整数であり、ｃは２～２０の整数である。以下同様。）である。 Among monomers B having a crosslinkable group, specific examples of monomers having a hydroxy group 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). More specifically, 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.
Provided that 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.
　単量体Ｂ（例えば、式：Ｘ’－Ｙ’－ＯＨの単量体と式：Ｘ’－Ｚ’－ＯＨの単量体）の他の具体例としては、下記化合物が挙げられる（ただし、下記式中の－ｃｙｃｌｏＣ６Ｈ１０－は、１，４－シクロヘキシレン基を示す。）。
　ＣＨ２＝ＣＨＯＣＨ２－ｃｙｃｌｏＣ６Ｈ１０－ＣＨ２ＯＨ、
　ＣＨ２＝ＣＨＣＨ２ＯＣＨ２－ｃｙｃｌｏＣ６Ｈ１０－ＣＨ２ＯＨ、
　ＣＨ２＝ＣＨＯＣ９Ｈ１８ＯＨ、
　ＣＨ２＝ＣＨＣＨ２ＯＣ９Ｈ１８ＯＨ、
　ＣＨ２＝ＣＨＯ－ＣａＨ２ａ－（ＯＣｂＨ２ｂ）ｃ－ＯＨ、
　ＣＨ２＝ＣＨＣＨ２Ｏ－ＣａＨ２ａ－（ＯＣｂＨ２ｂ）ｃ－ＯＨ、
　ＣＨ２＝ＣＨＯＣＨ２－ｃｙｃｌｏＣ６Ｈ１０－ＣａＨ２ａ－（ＯＣｂＨ２ｂ）ｃ－ＯＨ。 Other specific examples of the monomer B (for example, a monomer of the formula: X′-Y′-OH and a monomer of the formula: X′-Z′-OH) include the following compounds (provided that In the following formulae, -cycloC 6 H 10 -represents a 1,4-cyclohexylene group).
CH 2 = CHOCH 2 -cycloC 6 H 10 -CH 2 OH,
CH 2 = CHCH 2 OCH 2 -cycloC 6 H 10 -CH 2 OH,
CH 2 = CHOC 9 H 18 OH ,
CH 2 = CHCH 2 OC 9 H 18 OH,
CH 2 = CHO—C a H 2a — (OC b H 2b ) c —OH,
CH 2 ═CHCH 2 O—C a H 2a — (OC b H 2b ) c —OH,
CH 2 = CHOCH 2 -cycloC 6 H 10 -C a H 2a - (OC b H 2b) c -OH.
　単量体Ｂに基づく単位の含有量は、含フッ素重合体の全単位（１００ｍｏｌ％）に対して、５～２０ｍｏｌ％が好ましい。
　なお、単量体Ｂに由来する架橋性基は、絶縁被膜中においては、他の成分と反応していてもよい。たとえば、架橋性基は、架橋性基と反応する基を２個以上有する架橋剤と反応して、絶縁被膜中に架橋構造が形成されていてもよい。
　つまり、絶縁被膜中において、含フッ素重合体は架橋構造を有していてもよい。 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.
Note that the crosslinkable group derived from the monomer B may react with other components in the insulating coating. For example, 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.
　「他の単位」の第三の態様としては、フルオロオレフィンに基づく単位と上記単量体Ａに基づく単位と上記単量体Ｂに基づく単位以外の単位が挙げられる。該単位を形成する単量体の具体例としては、ノニルビニルエーテル、２－エチルヘキシルビニルエーテル、ヘキシルビニルエーテル、エチルビニルエーテル、ｎ－ブチルビニルエーテル、ｔｅｒｔ－ブチルビニルエーテル等のアルキルビニルエーテル、エチルアリルエーテル、ヘキシルアリルエーテル等のアルキルアリルエーテル、アルキルビニルエステル、アルキルアリルエステル、エチレン、プロピレン、イソブチレン等が挙げられる。 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. Specific examples of 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. And alkyl allyl ether, alkyl vinyl ester, alkyl allyl ester, ethylene, propylene, isobutylene and the like.
　本発明における含フッ素重合体の具体例は、フルオロオレフィンに基づく単位と、単量体Ａに基づく単位と、単量体Ｂに基づく単位とを有し、含フッ素重合体の全単位（１００ｍｏｌ％）に対する含有量が、好ましくは、順に、２０～８０ｍｏｌ％、５～４０ｍｏｌ％、５～３０ｍｏｌ％であり、より好ましくは、順に、３０～６０ｍｏｌ％、１０～３０ｍｏｌ％、５～２０ｍｏｌ％である、架橋構造を有する含フッ素重合体が挙げられる。 Specific examples of 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. ) Is preferably 20 to 80 mol%, 5 to 40 mol%, and 5 to 30 mol% in order, and more preferably 30 to 60 mol%, 10 to 30 mol%, and 5 to 20 mol% in order. And a fluorine-containing polymer having a crosslinked structure.
（金属塩）
　金属塩は、絶縁被膜付き電磁鋼板の防錆性を向上させる成分であれば、特に限定されず、リン酸、硝酸、炭酸、硫酸、ヘキサフルオロケイ酸、ヘキサフルオロチタン酸、およびヘキサフルオロジルコン酸から選ばれる少なくとも１種の無機酸の金属塩、または、蟻酸、酢酸、シュウ酸、乳酸、マロン酸、および酒石酸から選ばれる少なくとも１種の有機酸の金属塩が好ましい。無機酸は、絶縁被膜付き電磁鋼板の防錆性の観点から、リン酸が好ましい。
　金属塩の金属は、Ｌｉ、Ａｌ、Ｍｇ、Ｃａ、Ｓｒ、Ｔｉ、Ｎｉ、Ｍｎ、Ｃｏ、Ｚｒ、Ｆｅ、ＣｕまたはＡｇが好ましく、絶縁被膜付き電磁鋼板の防錆性の観点から、Ａｌが特に好ましい。
　金属塩は、電磁鋼板を腐食させうる酸化成分（通常、大気中の水分、酸素および二酸化炭素）を還元しうる還元性金属塩が好ましく、還元により電磁鋼板の表面に犠牲層を形成して電磁鋼板の腐食を抑制しうる還元性金属塩が特に好ましい。 (Metal salt)
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. preferable.
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.
　絶縁被膜には、上述した含フッ素重合体および金属塩以外の他の成分が含まれていてもよく、たとえば、後述する水系表面処理剤に含まれていてもよい他の成分が挙げられる。 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.
　絶縁被膜中における含フッ素重合体の含有量は特に制限されないが、絶縁被膜全質量に対して、０．０１～２０．０質量％が好ましく、０．１～１８．０質量％が特に好ましい。
　絶縁被膜中における金属塩の含有量は特に制限されないが、含フッ素重合体１００質量部に対して、１～１０００質量部が好ましく、１０～７００質量部が特に好ましい。金属塩の含有量が、上記範囲の下限値以上であれば、絶縁被膜付き電磁鋼板の防錆性に優れ、上記範囲の上限値以下であれば、絶縁被膜の外観に優れる。 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.
　絶縁被膜の付着量は特に制限されないが、電磁鋼板の片面あたりの付着量として、０．１～１０００ｇ／ｍ２が好ましく、０．５～５００ｇ／ｍ２が特に好ましい。 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.
＜絶縁被膜の製造方法＞
　絶縁被膜の製造方法は特に制限されず、公知の方法を採用することができる。例えば、上述した含フッ素重合体および金属塩を含む組成物を電磁鋼板上に塗布して、絶縁被膜を製造する方法や、含フッ素重合体および金属塩を含む組成物を溶融させて各種成形方法（例えば、押出し成形法）により電磁鋼板上に絶縁被膜を製造する方法等が挙げられる。なかでも、本発明では、下記する水系表面処理剤を用いる方法が好ましい。以下、水系表面処理剤を用いる方法について詳述する。 <Method for producing insulating coating>
The manufacturing method of an insulating film is not specifically limited, A well-known method is employable. For example, a method for producing an insulating film by applying the above-mentioned composition containing a fluoropolymer and a metal salt on a magnetic steel sheet, and various forming methods by melting a composition containing a fluoropolymer and a metal salt Examples thereof include a method of producing an insulating coating on an electromagnetic steel sheet (for example, an extrusion molding method). Of these, in the present invention, the following method using an aqueous surface treating agent is preferable. Hereinafter, the method using an aqueous surface treating agent will be described in detail.
（水系表面処理剤）
　水系表面処理剤は、電磁鋼板の表面に絶縁被膜を形成するために用いられる、水を含む表面処理剤であって、フルオロオレフィンに基づく単位、ビニルエーテル、アリルエーテルまたはカルボン酸ビニルであって、脂環式アルキル基を有する単量体Ａに基づく単位、および、ビニルエーテル、アリルエーテルまたはカルボン酸ビニルであって、水酸基、カルボキシ基およびアミノ基から選ばれる少なくとも１種の架橋性基を有する単量体Ｂに基づく単位を有する含フッ素重合体と、架橋剤と、金属塩とを含む。 (Aqueous surface treatment agent)
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.
　水系表面処理剤における含フッ素重合体を構成するそれぞれの単位（フルオロオレフィンに基づく単位、ビニルエーテル、アリルエーテルまたはカルボン酸ビニルであって、脂環式アルキル基を有する単量体Ａに基づく単位、および、ビニルエーテル、アリルエーテルまたはカルボン酸ビニルであって、水酸基、カルボキシ基およびアミノ基から選ばれる少なくとも１種の架橋性基を有する単量体Ｂに基づく単位）およびその好ましい態様、並びに、それぞれの単位の含フッ素重合体の全単位（１００ｍｏｌ％）に対する含有量の好ましい範囲は、上述した絶縁被膜に含まれる含フッ素重合体の説明の通りである。 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.
　含フッ素重合体が、架橋性基としてヒドロキシ基を有する場合には、含フッ素重合体の水酸基価は２０ｍｇＫＯＨ／ｇ以上が好ましく、４０ｍｇＫＯＨ／ｇ以上が特に好ましい。この場合、含フッ素重合体の水酸基価が上記下限値以上であれば、架橋剤との反応によって、絶縁被膜の耐溶剤性等が格段に向上する。上記水酸基価は、特に限定されないが、２００ｍｇＫＯＨ／ｇ以下が好ましい。 When the fluorine-containing polymer has a hydroxy group as a crosslinkable group, 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.
　また、水系表面処理剤に含まれる金属塩の定義およびその好ましい態様も、上述した絶縁被膜に含まれる金属塩の説明の通りである。 In addition, the definition of 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.
　水系表面処理剤に含まれる架橋剤は、含フッ素重合体の架橋性基と反応しうる基を２個以上有し、含フッ素重合体を架橋させる化合物であれば、特に限定されない。
　架橋剤は、含フッ素重合体中の架橋性基を有する単位の種類によって、適宜選択される。たとえば、含フッ素重合体に含まれる架橋性基がヒドロキシ基である場合には、イソシアネート基を２個以上有する化合物が好ましく、含フッ素重合体に含まれる架橋性基がアミノ基である場合にはイソシアネート基を２個以上有する化合物が好ましく、含フッ素重合体に含まれる架橋性基がカルボキシ基である場合にはアミノ基を２個以上有する化合物が好ましい。
　イソシアネート基を２個以上有する化合物としては、公知のイソシアネート系硬化剤、公知のブロック化イソシアネート系硬化剤などを使用できる。また、アミノ基を２個以上有する化合物としては、公知のアミノ樹脂を使用できる。なお、架橋剤は、自己架橋性を有する硬化剤であってもよい。 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. When the crosslinkable group contained in the fluoropolymer is a carboxy group, a compound having two or more amino groups is preferred.
As the compound having two or more isocyanate groups, a known isocyanate curing agent, a known blocked isocyanate curing agent, or the like can be used. Moreover, 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.
　水系表面処理剤において、含フッ素重合体の固形分濃度は、０．１～５０．０質量％であるのが好ましく、０．２～４０．０質量％であるのが特に好ましい。固形分濃度が上記範囲の下限値以上であれば、歪取り焼鈍後の滑り性が優れる。固形分濃度が上記範囲の上限値以下であれば、絶縁被膜の電磁鋼板への密着性が優れる。
　なお、後述するように、水系表面処理剤が含フッ素重合体以外の重合体（たとえば、アクリル樹脂等）を含む場合において、水系表面処理剤における含フッ素重合体と含フッ素重合体以外の重合体との合計の固形分濃度は上記した範囲内であるのが好ましい。 In the aqueous surface treatment agent, 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.
As will be described later, when 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.
　水系表面処理剤は、含フッ素重合体１００質量部に対して、金属塩を１～１０００質量部含むのが好ましく、１０～７００質量部含むのが特に好ましい。金属塩の含有量が、上記範囲の下限値以上であれば絶縁被膜付き電磁鋼板の防錆性に優れ、上記範囲の上限値以下であれば絶縁被膜の外観特性に優れる。 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.
　水系表面処理剤において、架橋剤の含有量は、含フッ素重合体１００質量部に対して、０．１～５０．０質量部が好ましく、０．５～３０．０質量部が特に好ましい。架橋剤の含有量が上記範囲の下限値以上であれば、絶縁被膜の耐水性に優れ、上記範囲の上限値以下であれば、絶縁被膜と電磁鋼板との密着性に優れる。 In the aqueous surface treatment agent, 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.
　水系表面処理剤は、含フッ素重合体と架橋剤と金属塩以外の他の成分を、必要に応じて含んでいてもよい。
　他の成分としては、有機溶媒、含フッ素重合体以外の重合体、乳化剤、無機系着色顔料、有機系着色顔料、体質顔料、硬化触媒、可塑剤、防腐剤、防黴剤、消泡剤、レベリング剤、顔料分散剤、沈降防止剤、たれ防止剤、艶消し剤、紫外線吸収剤、酸化防止剤、造膜助剤、増粘剤等が挙げられる。 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.
　なかでも、水系表面処理剤が造膜助剤を含む場合には、被膜外観、耐水性、電磁鋼板への密着性、防錆性等の物性により優れる絶縁被膜が得られる。造膜助剤としては、たとえば、ジプロピレングリコールモノｎ－ブチルエーテル、ジエチレングリコールモノエチルエーテルアセテート、２，２，４－トリメチル－１，３ペンタジオールモノ（２－メチルポロピオネート）、ジエチルングリコールジエチルエーテル等が挙げられる。 In particular, when 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. Examples of 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.
　有機溶媒の具体例としては、アルコール（メタノール、エタノール、ｎ－プロパノール、イソプロパノール、ｎ－ブタノール、イソブタノール、第２級ブタノール、第３級ブタノール、ペンタノール等）、セロソルブ（メチルセロソルブ、エチルセロソルブ、イソプロピルセロソルブ、ブチルセロソルブ、第２級ブチルセロソルブ等）、プロピレングリコール誘導体（プロピレングリコールメチルエーテル、ジプロピレングリコールメチルエーテル、プロピレングリコールメチルエーテルアセテート等）、エチレングリコールエチルエーテルアセテート、ケトン（アセトン、メチルエチルケトン、メチルイソブチルケトン等）、芳香族炭化水素（トルエン、キシレン等）が挙げられる。 Specific examples of the organic solvent 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.).
（製造手順）
　絶縁被膜付き電磁鋼板は、上記水系表面処理剤を電磁鋼板の表面に、ロールコータ等を用いた塗布法、スプレー法、ディップ法等の手段によって接触させた後、必要に応じて、加熱（焼き付け）処理して製造するのが好ましい。該処理を実施することにより、含フッ素重合体と架橋剤とが反応して、絶縁被膜中において架橋構造が形成される。
　加熱温度は、たとえば、１５０～４００℃であり、加熱時間は、たとえば、１５～１２０秒間である。 (Manufacturing procedure)
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. By carrying out the treatment, 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., and the heating time is, for example, 15 to 120 seconds.
＜絶縁被膜付き電磁鋼板＞
　上記絶縁被膜付き電磁鋼板は高温湿潤環境下での耐水性および防錆性に優れ、絶縁被膜の電磁鋼板への密着性に優れ、かつ、絶縁被膜の外観特性にも優れる。
　本発明の絶縁被膜付き電磁鋼板は、モーター（具体的には、モーターのステーターおよびローター）、トランスのＥＩコア等に好ましく適用でき、モーターが好ましい。
　より具体的には、本発明の絶縁被膜付き電磁鋼板は、発電所の発電機、超高圧変電所および一次、二次変電所の変圧器、工場の動力用モーターおよび変圧器、列車関係の電車用モーターおよび冷房用モーター、ビルの変圧器、冷房機、空調用モーター、道路照明の安定器、蛍光灯の安定器（トランスの一種）、洗濯機および脱水機用モーター、フロッピーディスクドライブ内のフロッピーを回転させるモーターおよびヘッドを動かすステッピングモーター、髭そりシェーバーのモーター、冷蔵庫およびエアコンのコンプレッサー用モーター、テレビの電源トランス、ハイブリッドカーのモーターの鉄芯等に使用できる。 <Electromagnetic steel sheet with insulation coating>
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.
More specifically, 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.
　以下、実施例を示して本発明を詳細に説明する。ただし、本発明は以下の記載によっては限定されない。なお、以下の例における略号は以下のとおりである。 Hereinafter, the present invention will be described in detail with reference to examples. However, the present invention is not limited by the following description. In addition, the symbol in the following examples is as follows.
　ＥＶＥ：エチルビニルエーテル
　ＣＨＶＥ：シクロヘキシルビニルエーテル
　ＣＭ－ＥＯＶＥ：ＣＨ２＝ＣＨＯＣＨ２－ｃｙｃｌｏＣ６Ｈ１０－ＣＨ２（ＯＣＨ２ＣＨ２）ｔＯＨ（数平均分子量：８３０）
　ＣＨＭＶＥ：ＣＨ２＝ＣＨＯＣＨ２－ｃｙｃｌｏＣ６Ｈ１０－ＣＨ２ＯＨ
　ＣＴＦＥ：クロロトリフルオロエチレン
　４－ＨＢＶＥ：４－ヒドロキシブチルビニルエーテル
　２－ＥＨＶＥ：２－エチルへキシルビニルエーテル
　ＰＶＤＦ：ポリビニリデンフルオリド EVE: ethyl vinyl ether CHVE: cyclohexyl vinyl ether CM-EOVE: CH 2 = CHOCH 2 -cycloC 6 H 10 -CH 2 (OCH 2 CH 2 ) t OH (number average molecular weight: 830)
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
（調製例１）
　以下のようにして、含フッ素重合体（１）を含む水性液（１）を調製した。
　内容積２５００ｍＬの撹拌機付きステンレス製オートクレーブ中に、水（１２８０ｇ）、ＥＶＥ（１８５ｇ）、ＣＨＶＥ（２４４ｇ）、ＣＭ－ＥＯＶＥ（４７ｇ）、ＣＨＭＶＥ（１９４ｇ）、イオン交換水（１２８０ｇ）、炭酸カリウム（２．０ｇ）、過硫酸アンモニウム（１．３ｇ）、ノニオン性乳化剤（日本乳化剤社製、Ｎｅｗｃｏｌ（登録商標）－２３２０）（３３ｇ）、および、アニオン性乳化剤（ラウリル硫酸ナトリウム）（１．４ｇ）を仕込み、オートクレーブを氷で冷却して、窒素ガスでオートクレーブ内が０．４ＭＰａＧになるよう加圧し脱気した。この加圧脱気を２回繰り返した。次に、オートクレーブ内が０．０９５ＭＰａＧとなるまで脱気して溶存空気を除去した後、オートクレーブ中にＣＴＦＥ（６６４ｇ）を仕込み、５０℃で２４時間反応を行った。２４時間反応を行った後、オートクレーブを水冷して反応を停止した。得られた反応液を室温まで冷却した後、未反応単量体をパージし、固形分濃度５０質量％の水性液（１）を得た。
　水性液（１）に含まれる含フッ素重合体（１）の水酸基価は５５ｍｇＫＯＨ／ｇであり、含フッ素重合体（１）中の各単位の比はＣＴＦＥ単位／ＣＭ－ＥＯＶＥ単位／ＣＨＭＶＥ単位／ＥＶＥ単位／ＣＨＶＥ単位＝５０／０．５／１０／２２．５／１７（モル比）であり、含フッ素重合体（１）のフッ素原子含有量は２４．３質量％であった。
　なお、含フッ素重合体（１）中の各単位の比は、１Ｈ－ＮＭＲや１３Ｃ－ＮＭＲでの分析により求められる。また、含フッ素重合体（１）のフッ素原子含有量は、以下の手順によって測定した。
　１）遠心分離により、水性液（１）から含フッ素重合体（１）を回収した。
　２）含フッ素重合体（１）と炭酸カリウムとまぶした後に、るつぼ中で、６００℃にて、１時間加熱分解させた。
　３）生成したフッ化カリウムを水に溶解させた水溶液のフッ素物イオン強度をイオン電極法により測定した。
　４）測定したフッ化物イオン強度と、フッ素濃度が既知であるポリテトラフルオロエチレン単独重合体のキャリブレーション値とから、含フッ素重合体（１）のフッ素原子含有量を算出した。 (Preparation Example 1)
An 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. This pressure degassing was repeated twice. Next, after deaeration until the inside of the autoclave became 0.095 MPaG and dissolved air was removed, CTFE (664 g) was charged into the autoclave and reacted at 50 ° C. for 24 hours. After reacting for 24 hours, the autoclave was cooled with water to stop the reaction. After cooling the obtained reaction liquid to room temperature, the unreacted monomer was purged to obtain an aqueous liquid (1) having a solid concentration of 50% by mass.
The hydroxyl value of the fluoropolymer (1) contained in the aqueous liquid (1) is 55 mgKOH / g, and the ratio of each unit in the fluoropolymer (1) is CTFE unit / CM-EOOVE unit / CHMVE unit / EVE unit / CHVE unit = 50 / 0.5 / 10 / 22.5 / 17 (molar ratio), and the fluorine atom content of the fluoropolymer (1) was 24.3 mass%.
The ratio of each unit in the fluoropolymer (1) can be determined by analysis with 1 H-NMR or 13 C-NMR. Moreover, the fluorine atom content of the fluoropolymer (1) was measured by the following procedure.
1) 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.
（調製例２）
　以下のようにして、含フッ素重合体（２）を含む水性液（２）を調製した。
　含フッ素重合体（旭硝子社製、ルミフロン（登録商標）フレーク、ＣＴＦＥ単位／ＥＶＥ単位／ＣＨＶＥ単位／４－ＨＢＶＥ単位＝５０／１５／１５／２０（モル比）、水酸基価：１００ｍｇＫＯＨ／ｇ、質量平均分子量：７０００）を、メチルエチルケトン（ＭＥＫ）に溶解させて固形分６０質量％のワニスを得た。
　このワニス（３００ｇ）に、無水こはく酸（４．８ｇ）、および触媒としてトリエチルアミン（０．０７２ｇ）を加え、７０℃で６時間反応させエステル化した。反応液の赤外吸収スペクトルを測定したところ、反応前に観測された無水酸の特性吸収（１８５０ｃｍ－１、１７８０ｃｍ－１）が反応後では消失しており、カルボン酸（１７１０ｃｍ－１）およびエステル（１７３５ｃｍ－１）の吸収が観測された。エステル化後の含フッ素重合体の水酸基価は８５ｍｇ／ＫＯＨ、酸価は１５ｍｇＫＯＨ／ｇであった。
　次に、エステル化後の含フッ素重合体に、トリエチルアミン（４．９ｇ）を加え室温で２０分撹拌してカルボン酸を中和し、イオン交換水（１８０ｇ）を徐々に加えた。
　最後に、メチルエチルケトンを減圧留去した。その後、得られた固形物とイオン交換水とを混合し、固形分濃度５０質量％の水性液（２）を得た。
　水性液（２）に含まれる含フッ素重合体（２）の各単位の比は、ＣＴＦＥ単位／ＥＶＥ単位／ＣＨＶＥ単位／４－ＨＢＶＥ単位／エステル化された４－ＨＢＶＥ単位＝５０／１５／１５／１７／３（モル比）であった。エステル化された４－ＨＢＶＥ単位のうち、トリエチルアミンで中和された割合は７０モル％であった。
　なお、含フッ素重合体（２）中の各単位の比は、１Ｈ－ＮＭＲや１３Ｃ－ＮＭＲでの分析により求められ、調製例１と同様にして求めた含フッ素重合体（２）のフッ素原子含有量は２５．６質量％であった。 (Preparation Example 2)
An aqueous liquid (2) containing the fluoropolymer (2) was prepared as follows.
Fluoropolymer (Asahi Glass Co., Ltd., Lumiflon (registered trademark) flakes, CTFE unit / EVE unit / CHVE unit / 4-HBVE unit = 50/15/15/20 (molar ratio)), hydroxyl value: 100 mgKOH / g, mass (Molecular weight: 7000) was dissolved in methyl ethyl ketone (MEK) to obtain a varnish having a solid content of 60% by mass.
To this varnish (300 g), succinic anhydride (4.8 g) and triethylamine (0.072 g) as a catalyst were added and reacted at 70 ° C. for 6 hours for esterification. When the infrared absorption spectrum of the reaction solution was measured, the characteristic absorption (1850 cm −1 , 1780 cm −1 ) of the acid anhydride observed before the reaction disappeared after the reaction, and the carboxylic acid (1710 cm −1 ) and ester Absorption of (1735 cm −1 ) was observed. The hydroxyl value of the fluoropolymer after esterification was 85 mg / KOH, and the acid value was 15 mgKOH / g.
Next, triethylamine (4.9 g) was added to the esterified fluoropolymer, and the mixture was stirred at room temperature for 20 minutes to neutralize the carboxylic acid, and ion-exchanged water (180 g) was gradually added.
Finally, methyl ethyl ketone was distilled off under reduced pressure. Thereafter, the obtained solid and ion-exchanged water were mixed to obtain an aqueous liquid (2) having a solid concentration of 50% by mass.
The ratio of each unit of the fluoropolymer (2) contained in the aqueous liquid (2) was as follows: CTFE unit / EVE unit / CHVE unit / 4-HBVE unit / esterified 4-HBVE unit = 50/15/15 / 17/3 (molar ratio). Among the esterified 4-HBVE units, 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.
　（調製例３）
　以下のようにして、含フッ素重合体（３）を含む水性液（３）を調製した。
　内容積２５００ｍＬの撹拌機付きステンレス製オートクレーブ中に、水（１２８０ｇ）、ＣＨＶＥ（４１５ｇ）、２－ＥＨＶＥ（２３０ｇ）、ＣＭ－ＥＯＶＥ（２１ｇ）、ＣＨＭＶＥ（３４ｇ）、イオン交換水（１２８０ｇ）、炭酸カリウム（３．０ｇ）、過硫酸アンモニウム（５．４ｇ）、ノニオン性乳化剤（日本乳化剤社製、Ｎｅｗｃｏｌ（登録商標）－２３２０）（３３ｇ）、および、アニオン性乳化剤（ラウリル硫酸ナトリウム）（１．４ｇ）を仕込み、オートクレーブを氷で冷却して、窒素ガスでオートクレーブ内を０．４ＭＰａＧになるよう加圧し脱気した。この加圧脱気を２回繰り返した。次に、オートクレーブ内が０．０９５ＭＰａＧとなるまで脱気して溶存空気を除去した後、ＣＴＦＥ（５８０ｇ）を仕込み、５０℃で２４時間反応を行った。２４時間反応を行った後、オートクレーブを水冷して反応を停止した。得られた反応液を室温まで冷却した後、未反応単量体をパージし、固形分濃度５０質量％の水性液（３）を得た。
　水性液（３）に含まれる含フッ素重合体（３）の水酸基価は１０ｍｇＫＯＨ／ｇであった。含フッ素重合体（３）中の各単位の比は、ＣＴＦＥ単位／ＣＭ－ＥＯＶＥ単位／ＣＨＭＶＥ単位／ＣＨＶＥ単位／２－ＥＨＶＥ単位＝５０／０．２５／２／３３／１４．７５（モル比）であった。
　なお、含フッ素重合体（３）中の各単位の比は、１Ｈ－ＮＭＲや１３Ｃ－ＮＭＲでの分析により求められ、調製例１と同様にして求めた含フッ素重合体（３）のフッ素原子含有量は２２．２質量％であった。 (Preparation Example 3)
An aqueous liquid (3) containing the fluoropolymer (3) was prepared as follows.
In a stainless steel autoclave with a stirrer having an internal volume of 2500 mL, water (1280 g), CHVE (415 g), 2-EHVE (230 g), CM-EOVE (21 g), CHMVE (34 g), ion-exchanged water (1280 g), carbonic acid Potassium (3.0 g), ammonium persulfate (5.4 g), nonionic emulsifier (Nippon Emulsifier, Newcol (registered trademark) -2320) (33 g), and anionic emulsifier (sodium lauryl sulfate) (1.4 g ), The autoclave was cooled with ice, and the inside of the autoclave was pressurized with nitrogen gas to 0.4 MPaG and degassed. This pressure degassing was repeated twice. Next, after deaeration until the inside of the autoclave became 0.095 MPaG to remove dissolved air, CTFE (580 g) was charged, and the reaction was performed at 50 ° C. for 24 hours. After reacting for 24 hours, the autoclave was cooled with water to stop the reaction. After cooling the obtained reaction liquid to room temperature, the unreacted monomer was purged to obtain an aqueous liquid (3) having a solid content concentration of 50% by mass.
The hydroxyl value of the fluoropolymer (3) contained in the aqueous liquid (3) was 10 mgKOH / g. The ratio of each unit in the fluoropolymer (3) is CTFE units / CM-EOVE units / CHMVE units / CHVE units / 2-EHVE units = 50 / 0.25 / 2/33 / 14.75 (molar ratio). )Met.
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.
（実施例１）
　リン酸アルミニウム（１０．０ｇ）、調製例１で得た含フッ素重合体（１）の水性液（１）（５．０ｇ）、造膜助剤であるジプロピレングリコールモノｎ－ブチルエーテル（０．４ｇ）、増粘剤（アクゾノーベル社製、ベルモドール（登録商標）２１５０）（０．０１ｇ）、水分散型イソシアネート系硬化剤（住化バイエル社製、バイヒジュール（登録商標）３１００）（０．６ｇ）、および、イオン交換水（８３．９９ｇ）を混合し、水系表面処理剤（１）を調製した。水系表面処理剤（１）中における含フッ素重合体（１）の固形分濃度は２．５質量％であった。
　得られた水系表面処理剤（１）を板厚０．５ｍｍの電磁鋼板の両面に、焼き付け後の絶縁被膜の付着量（片面あたりの付着量）が１．０ｇ／ｍ２となるようにロールコータで塗布し、その後、熱風炉で最高到達温度が２７０℃となるように、３０秒間加熱して架橋構造を有する含フッ素重合体を含む絶縁被膜を電磁鋼板の両表面に形成した。 (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. After coating with a coater, 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.
　なお、別途作製した含フッ素重合体（１）のシートの膜厚１μｍあたりの水蒸気透過率、膜厚１μｍあたりの酸素透過率、および、膜厚１μｍあたりの二酸化炭素透過率は、それぞれ、１．８ｇ／ｍ２・ｄａｙ、０．０２ｍｏｌ／ｍ２・ｓ・Ｐａ、および、０．０２ｍｏｌ／ｍ２・ｓ・Ｐａであった。上記含フッ素重合体（１）のシートを作製する際には、含フッ素重合体（１）と水分散型イソシアネート系硬化剤（住化バイエル社製、バイヒジュール（登録商標）３１００）とを用いた。含フッ素重合体（１）のシート中には架橋構造が含まれていた。含フッ素重合体（１）と水分散型イソシアネート系硬化剤との使用量比は、上記水系表面処理剤（１）中での使用量比と同じであった。 In addition, the water vapor transmission rate per 1 μm film thickness, the oxygen transmission rate per 1 μm film thickness, and the carbon dioxide transmission rate per 1 μm 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. When the sheet of the fluoropolymer (1) was prepared, 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).
（実施例２）
　水性液（１）を水性液（２）に変更し、含フッ素重合体（２）の固形分濃度を２．５質量％とした以外は、実施例１と同様にして水系表面処理剤（２）を調製し、それを用いて架橋構造を有する含フッ素重合体を含む絶縁被膜を電磁鋼板の両表面に形成した。 (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.
　なお、別途作製した含フッ素重合体（２）のシートの膜厚１μｍあたりの水蒸気透過率、膜厚１μｍあたりの酸素透過率、および、膜厚１μｍあたりの二酸化炭素透過率は、それぞれ、１．９ｇ／ｍ２・ｄａｙ、０．０３ｍｏｌ／ｍ２・ｓ・Ｐａ、および、０．０３ｍｏｌ／ｍ２・ｓ・Ｐａであった。上記含フッ素重合体（２）のシートを作製する際には、含フッ素重合体（２）と水分散型イソシアネート系硬化剤（住化バイエル社製、バイヒジュール（登録商標）３１００）とを用いた。含フッ素重合体（２）のシート中には架橋構造が含まれていた。含フッ素重合体（２）と水分散型イソシアネート系硬化剤との使用量比は、上記水系表面処理剤（２）中での使用量比と同じであった。 In addition, the water vapor transmission rate per 1 μm film thickness, the oxygen transmission rate per 1 μm film thickness, and the carbon dioxide transmission rate per 1 μm 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. When the sheet of the fluoropolymer (2) was prepared, 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).
（比較例１）
　調製例１の水性液（１）を、ＰＶＤＦとアクリル樹脂を含む水性液（Ａｒｋｅｍａ社製、製品名「Ｋｙｎａｒ（登録商標）　Ａｑｕａｔｅｃ　ＦＭＡ－１２」（ＰＶＤＦ／アクリル樹脂＝５０／５０（質量比）、アクリル樹脂：メタクリル酸メチル単位／メタクリル酸エチル単位／メタクリル酸ブチル単位＝６０／２０／２０（モル比）、固形分濃度５０質量％、ＰＶＤＦのフッ素原子含有量：２９．５ｗｔ％、ＣＨＶＥ単位：０．０モル％。）に変更した以外は、実施例１と同様にして、固形分濃度（ＰＶＤＦとアクリル樹脂の合計濃度）が２．５質量％の水系表面処理剤（３）を調製し、それを用いてＰＶＤＦとアクリル樹脂とを含む絶縁被膜を電磁鋼板の両表面に形成した。
　なお、別途作製したＰＶＤＦのシート（ＰＶＤＦからなるシート）の膜厚１μｍあたりの水蒸気透過率、膜厚１μｍあたりの酸素透過率、および、膜厚１μｍあたりの二酸化炭素透過率は、それぞれ１９．６ｇ／ｍ２・ｄａｙ、０．５ｍｏｌ／ｍ２・ｓ・Ｐａ、および、０．６ｍｏｌ／ｍ２・ｓ・Ｐａであった。 (Comparative Example 1)
The aqueous liquid (1) of Preparation Example 1 was converted into an aqueous liquid containing PVDF and an acrylic resin (manufactured by Arkema, product name “Kynar (registered trademark) Aquatec FMA-12” (PVDF / acrylic resin = 50/50 (mass ratio)). , Acrylic resin: methyl methacrylate unit / ethyl methacrylate unit / butyl methacrylate unit = 60/20/20 (molar ratio), solid content concentration 50 mass%, fluorine atom content of PVDF: 29.5 wt%, CHVE unit : 0.0 mol%.) 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 μm film thickness, an oxygen transmission rate per 1 μm film thickness, and a carbon dioxide transmission rate per 1 μm film thickness of 19.6 g. / M 2 · day, 0.5 mol / m 2 · s · Pa, and 0.6 mol / m 2 · s · Pa.
（比較例２）
　水性液（１）を水性液（３）に変更し、さらに、水分散型イソシアネート系硬化剤を添加しなかった以外は、実施例１と同様にして、水系表面処理剤（４）を調製し、それを用いて架橋構造を有しない含フッ素重合体を含む絶縁被膜を電磁鋼板の両表面に形成した。 (Comparative Example 2)
An 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.
　なお、別途作製した含フッ素重合体（３）のシート（含フッ素重合体（３）からなるシート）の膜厚１μｍあたりの水蒸気透過率、膜厚１μｍあたりの酸素透過率、および、膜厚１μｍあたりの二酸化炭素透過率は、それぞれ、１．０ｇ／ｍ２・ｄａｙ、０．２ｍｏｌ／ｍ２・ｓ・Ｐａ、および、０．１ｍｏｌ／ｍ２・ｓ・Ｐａであった。 In addition, the water vapor transmission rate per film thickness of 1 μm, the oxygen transmission rate per film thickness of 1 μm, and the film thickness of 1 μm 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.
　それぞれの例で得られた絶縁被膜付き電磁鋼板の被膜外観、耐水性（耐白化性）、密着性、および、防錆性を以下の方法により評価した。それぞれの絶縁被膜に含まれる含フッ素重合体の物性を表１に、評価結果を表２に示す。 The coating appearance, water resistance (whitening resistance), adhesion, and rust resistance of the electrical steel sheet with insulating coating obtained in each example were evaluated by the following methods. Table 1 shows the physical properties of the fluoropolymer contained in each insulating film, and Table 2 shows the evaluation results.
（評価方法）
（１）被膜外観
　絶縁被膜付き電磁鋼板の試験片の絶縁被膜の外観を目視により観察して、下記の３段階で評価した。○が合格である。
　○：全面的に透明で、ヘイズが全く見られない。
　△：部分的に透明性の劣る部位がある。
　×：全面的に透明性が劣る。 (Evaluation methods)
(1) Appearance of coating The appearance of the insulating coating of the test piece of the electrical steel sheet with insulating coating was visually observed and evaluated in the following three stages. ○ is a pass.
○: Fully transparent and no haze is observed.
(Triangle | delta): There exists a site | part with inferior transparency partially.
X: Transparency is entirely inferior.
（２）耐水性（耐白化性）
　５０℃、９８％ＲＨに調整した恒温恒湿槽内に、絶縁被膜付き電磁鋼板の試験片を吊るし、７２時間経過後の絶縁被膜表面の状態を目視により評価した。○が合格である。
　　○：白化なし　　×：白化あり (2) Water resistance (whitening resistance)
A test piece of an electromagnetic steel sheet with an insulating coating was hung in a constant temperature and humidity chamber adjusted to 50 ° C. and 98% RH, and the state of the insulating coating surface after 72 hours was visually evaluated. ○ is a pass.
○: No whitening ×: Whitening
（３）密着性
　長さ５０ｍｍ、幅２５ｍｍの絶縁被膜付き電磁鋼板の試験片を、直径５ｍｍの鉄棒に巻き付け、巻き付けた外側の部分（絶縁被膜）についてテープ剥離試験を行って、電磁鋼板に残存した絶縁被膜の状況を目視により評価した。○が合格である。
　　○：被膜剥離なし　　×：被膜剥離発生 (3) 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
（４）防錆性
　絶縁被膜付き電磁鋼板の試験片を、５０℃、９５％ＲＨに調整した恒温恒湿槽内に８００時間暴露した後、表面錆の面積率を目視で判定した。○が合格である。
　　○：表面錆の面積率が１０％以下　　×：表面錆の面積率が１０％超 (4) Rust prevention property After exposing the test piece of the electrical steel sheet with an insulating coating to a constant temperature and humidity chamber adjusted to 50 ° C. and 95% RH for 800 hours, the area ratio of the surface rust was visually determined. ○ is a pass.
○: Area ratio of surface rust is 10% or less ×: Area ratio of surface rust exceeds 10%
　表１中、「架橋構造」欄は、絶縁被膜中における含フッ素重合体の架橋構造の有無を表す。表１中、「水蒸気透過率」、「酸素透過率」、および、「二酸化炭素透過率」は、各実施例および各比較例で作製した含フッ素重合体のシートの各測定値を表す。 In Table 1, the “crosslinked structure” column represents the presence or absence of a crosslinked structure of the fluoropolymer in the insulating coating. In Table 1, “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.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　上記表２に示すように、本発明の絶縁被膜付き電磁鋼板においては、所望の効果が得られることが確認された。
　一方、含フッ素重合体のシートの水蒸気透過率および酸素透過率が所定範囲外である比較例１、および、含フッ素重合体のシートの酸素透過率が所定範囲外である比較例２では、所望の効果が得られなかった。 As shown in Table 2 above, it was confirmed that the desired effect was obtained in the electrical steel sheet with an insulating coating of the present invention.
On the other hand, in Comparative Example 1 in which the water vapor transmission rate and oxygen transmission rate of the fluoropolymer sheet are outside the predetermined ranges, and in Comparative Example 2 in which the oxygen transmission rate of the fluoropolymer sheet is outside the predetermined ranges, the desired The effect of was not obtained.
　本発明の絶縁被膜付き電磁鋼板は、種々の用途に適用でき、たとえば、発電所の発電機、超高圧変電所および一次、二次変電所の変圧器、工場の動力用モーターおよび変圧器、列車関係の電車用モーターおよび冷房用モーター、ビルの変圧器、冷房機、空調用モーター、道路照明の安定器、蛍光灯の安定器（トランスの一種）、洗濯機および脱水機用モーター、フロッピー（登録商標）ディスクドライブ内のフロッピー（登録商標）を回転させるモーターおよびヘッドを動かすステッピングモーター、髭そりシェーバーのモーター、冷蔵庫およびエアコンのコンプレッサー用モーター、テレビの電源トランス、並びに、ハイブリッドカーのモーターの鉄芯等に使用できる。 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. Related 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.
　なお、２０１５年４月２０日に出願された日本特許出願２０１５－０８６２４８号の明細書、特許請求の範囲、図面、及び要約書の全内容をここに引用し、本発明の明細書の開示として、取り入れるものである。 The entire contents of the specification, claims, drawings, and abstract of Japanese Patent Application No. 2015-086248 filed on April 20, 2015 are cited herein as disclosure of the specification of the present invention. Incorporate.

Claims (13)

  1. 　電磁鋼板と、
    　前記電磁鋼板上に配置された、フルオロオレフィンに基づく単位を有する含フッ素重合体および金属塩を含む絶縁被膜を有する絶縁被膜付き電磁鋼板であって、
    　前記含フッ素重合体が、以下の要件１および要件２を満たすことを特徴とする絶縁被膜付き電磁鋼板。
    　要件１：前記含フッ素重合体をシート状とした際、含フッ素重合体シートの膜厚１μｍあたりの水蒸気透過率が０．０１～５ｇ／ｍ２・ｄａｙである。
    　要件２：前記含フッ素重合体をシート状とした際、含フッ素重合体シートの膜厚１μｍあたりの酸素透過率が０．２ｍｏｌ／ｍ２・ｓ・Ｐａ未満である。     Electrical steel sheet,
    An electrical steel sheet with an insulating coating having an insulating coating containing a fluoropolymer having a unit based on a fluoroolefin and a metal salt disposed on the electrical steel plate,
    An electrical steel sheet with an insulating coating, wherein the fluoropolymer satisfies the following requirements 1 and 2.
    Requirement 1: When the fluoropolymer is formed into a sheet, the water vapor transmission rate per 1 μm thickness of the fluoropolymer sheet is 0.01 to 5 g / m 2 · day.
    Requirement 2: When the fluoropolymer sheet is formed into a sheet, the oxygen permeability per 1 μm thickness of the fluoropolymer sheet is less than 0.2 mol / m 2 · s · Pa.
  2. 　前記含フッ素重合体が、さらに、以下の要件３を満たす、請求項１に記載の絶縁被膜付き電磁鋼板。
    　要件３：前記含フッ素重合体をシート状とした際、含フッ素重合体シートの膜厚１μｍあたりの二酸化炭素透過率が０．１ｍｏｌ／ｍ２・ｓ・Ｐａ未満である。     The electrical steel sheet with an insulating coating according to claim 1, wherein the fluoropolymer further satisfies the following requirement 3.
    Requirement 3: When the fluoropolymer is formed into a sheet, the carbon dioxide permeability per 1 μm thickness of the fluoropolymer sheet is less than 0.1 mol / m 2 · s · Pa.
  3. 　前記含フッ素重合体のフッ素原子含有量が１５～３０ｗｔ％である、請求項１または２に記載の絶縁被膜付き電磁鋼板。 3. The electrical steel sheet with an insulating coating according to claim 1, wherein the fluorine-containing polymer has a fluorine atom content of 15 to 30 wt%.
  4. 　前記含フッ素重合体が、ビニルエーテル、アリルエーテルまたはカルボン酸ビニルであって、脂環式アルキル基を有する単量体Ａに基づく単位を有する、請求項１～３のいずれかに１項に記載の絶縁被膜付き電磁鋼板。 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, according to any one of claims 1 to 3. Electrical steel sheet with insulation coating.
  5. 　前記単量体Ａに基づく単位の含有量が、前記含フッ素重合体の全単位（１００ｍｏｌ％）に対して、５～４０ｍｏｌ％である、請求項４に記載の絶縁被膜付き電磁鋼板。 The electrical steel sheet with an insulating coating according to claim 4, wherein the content of the unit based on the monomer A is 5 to 40 mol% with respect to the total unit (100 mol%) of the fluoropolymer.
  6. 　前記含フッ素重合体が、ビニルエーテル、アリルエーテルまたはカルボン酸ビニルであって、水酸基、カルボキシ基およびアミノ基から選ばれる少なくとも１種の架橋性基を有する単量体Ｂに基づく単位を有する、請求項１～５のいずれか１項に記載の絶縁被膜付き電磁鋼板。 The fluorine-containing polymer is a vinyl ether, allyl ether or vinyl carboxylate, and has a unit based on a monomer B having at least one crosslinkable group selected from a hydroxyl group, a carboxy group, and an amino group. 6. An electrical steel sheet with an insulating coating according to any one of 1 to 5.
  7. 　前記単量体Ｂに基づく単位の含有量が、前記含フッ素重合体の全単位（１００ｍｏｌ％）に対して、５～２０ｍｏｌ％である、請求項６に記載の絶縁被膜付き電磁鋼板。 The electrical steel sheet with an insulating coating according to claim 6, wherein the content of the unit based on the monomer B is 5 to 20 mol% with respect to the total unit (100 mol%) of the fluoropolymer.
  8. 　前記含フッ素重合体が、架橋構造を有する、請求項１～７のいずれか１項に記載の絶縁被膜付き電磁鋼板。 The electrical steel sheet with an insulating coating according to any one of claims 1 to 7, wherein the fluoropolymer has a crosslinked structure.
  9. 　請求項１～８のいずれか１項に記載の絶縁被膜付き電磁鋼板を有するモーター。 A motor having the electromagnetic steel sheet with an insulating coating according to any one of claims 1 to 8.
  10. 　電磁鋼板の表面に絶縁被膜を形成するために用いられる、水を含む水系表面処理剤であって、フルオロオレフィンに基づく単位、ビニルエーテル、アリルエーテルまたはカルボン酸ビニルであって、脂環式アルキル基を有する単量体Ａに基づく単位、並びに、ビニルエーテル、アリルエーテルまたはカルボン酸ビニルであって、水酸基、カルボキシ基およびアミノ基から選ばれる少なくとも１種の架橋性基を有する単量体Ｂに基づく単位を有する含フッ素重合体と、架橋剤と、金属塩と、を含むことを特徴とする水系表面処理剤。 An aqueous surface treatment agent containing water, used for forming an insulating film on the surface of an electrical steel sheet, comprising a unit based on fluoroolefin, vinyl ether, allyl ether or vinyl carboxylate, having an alicyclic alkyl group A unit based on the monomer A, and a unit based on the monomer B which is vinyl ether, allyl ether or vinyl carboxylate and has at least one crosslinkable group selected from a hydroxyl group, a carboxy group and an amino group. An aqueous surface treating agent comprising: a fluorine-containing polymer having a crosslinking agent; and a metal salt.
  11. 　前記架橋剤が、イソシアネート基またはアミノ基を２個以上有する化合物である、請求項１０に記載の水系表面処理剤。 The aqueous surface treating agent according to claim 10, wherein the crosslinking agent is a compound having two or more isocyanate groups or amino groups.
  12. 　前記金属塩が、リン酸、硝酸、炭酸、硫酸、ヘキサフルオロケイ酸、ヘキサフルオロチタン酸、およびヘキサフルオロジルコン酸から選ばれる少なくとも１種の無機酸の金属塩、または、蟻酸、酢酸、シュウ酸、乳酸、マロン酸、および酒石酸からなる群から選ばれる少なくとも１種の有機酸の金属塩である、請求項１０または１１に記載の水系表面処理剤。 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, oxalic acid The aqueous surface treating agent according to claim 10 or 11, which is a metal salt of at least one organic acid selected from the group consisting of lactic acid, malonic acid, and tartaric acid.
  13. 　前記金属塩の金属が、Ｌｉ、Ａｌ、Ｍｇ、Ｃａ、Ｓｒ、Ｔｉ、Ｎｉ、Ｍｎ、Ｃｏ、Ｚｒ、Ｆｅ、ＣｕまたはＡｇである、請求項１０～１２のいずれか１項に記載の水系表面処理剤。 The water-based surface according to any one of claims 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. Processing agent.
PCT/JP2016/062276 2015-04-20 2016-04-18 Electromagnetic steel sheet with insulating coating and aqueous surface treatment agent WO2016171104A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2017514114A JP6733665B2 (en) 2015-04-20 2016-04-18 Magnetic steel sheet with insulating coating and water-based surface treatment agent

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2015-086248 2015-04-20
JP2015086248 2015-04-20

Publications (1)

Publication Number Publication Date
WO2016171104A1 true WO2016171104A1 (en) 2016-10-27

Family

ID=57143998

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2016/062276 WO2016171104A1 (en) 2015-04-20 2016-04-18 Electromagnetic steel sheet with insulating coating and aqueous surface treatment agent

Country Status (2)

Country Link
JP (1) JP6733665B2 (en)
WO (1) WO2016171104A1 (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023054222A1 (en) * 2021-09-30 2023-04-06 富士フイルム株式会社 Composition, cured product, method for producing cured product, structure, and device
WO2023145800A1 (en) * 2022-01-26 2023-08-03 日本製鉄株式会社 Non-oriented electromagnetic steel sheet

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003012826A (en) * 2001-06-29 2003-01-15 Nippon Steel Corp Film for coating steel material and resin coated steel material
WO2012057168A1 (en) * 2010-10-29 2012-05-03 新日本製鐵株式会社 Electromagnetic steel sheet and process for production thereof
WO2013153020A2 (en) * 2012-04-12 2013-10-17 Nuovo Pignone Srl Method for preventing corrosion and component obtained by means of such

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003012826A (en) * 2001-06-29 2003-01-15 Nippon Steel Corp Film for coating steel material and resin coated steel material
WO2012057168A1 (en) * 2010-10-29 2012-05-03 新日本製鐵株式会社 Electromagnetic steel sheet and process for production thereof
WO2013153020A2 (en) * 2012-04-12 2013-10-17 Nuovo Pignone Srl Method for preventing corrosion and component obtained by means of such

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023054222A1 (en) * 2021-09-30 2023-04-06 富士フイルム株式会社 Composition, cured product, method for producing cured product, structure, and device
WO2023145800A1 (en) * 2022-01-26 2023-08-03 日本製鉄株式会社 Non-oriented electromagnetic steel sheet

Also Published As

Publication number Publication date
JP6733665B2 (en) 2020-08-05
JPWO2016171104A1 (en) 2018-03-29

Similar Documents

Publication Publication Date Title
US10619069B2 (en) Chemical conversion-treated steel sheet and method for producing same, and chemical conversion treatment solution
TWI478365B (en) Solar battery module with backplane and solar module
TWI490114B (en) Chemically converted plated steel plate and fabricating method thereof
TWI500500B (en) Chemically converted plated steel plate and fabrication method thereof
DE102008059014A1 (en) Process for coating metal strips
JP6080670B2 (en) Ground treatment composition for coated steel sheet, plated steel sheet subjected to ground treatment and method for producing the same, painted steel sheet and method for producing the same
JP2007197824A (en) Electromagnetic steel sheet with insulating coating film
TWI632253B (en) Chemically treated steel sheet and manufacturing method thereof, and chemical treatment liquid
JP2007197820A (en) Electromagnetic steel sheet having insulating coating film and method for producing same
JP6733665B2 (en) Magnetic steel sheet with insulating coating and water-based surface treatment agent
JP5674605B2 (en) Chemical conversion treated steel sheet and method for producing the same
JP6404977B2 (en) Heat-resistant adhesive insulating coating composition and electrical steel sheet with insulating coating
JP4608600B2 (en) Electrical steel sheet having an insulating coating excellent in thermal conductivity and method for producing the same
JP5727543B2 (en) Magnesium-based metal member and method for producing magnesium-based metal member
WO2019146584A1 (en) Anti-rust treatment solution for welded steel pipes, chemical conversion treatment method for welded steel pipe, welded steel pipe and formed product of welded steel pipes
KR101373580B1 (en) Backsheets Containing Coating Layers with High Barrier Properties for Photovoltaic Modules
JP6828786B2 (en) Aqueous dispersion, coating film and painted article, and method for producing aqueous dispersion
WO2015145514A1 (en) Chemical conversion coated steel sheet, and manufacturing method and chemical conversion solution therefor
WO2019146583A1 (en) Anti-rust treatment solution for end face of plated steel sheet, method for chemical conversion treatment of end face of plated steel sheet, chemical conversion treated steel sheet, and molded article
JP5678808B2 (en) Fluorine-containing copolymer composition for water-based paint
JP5674606B2 (en) Chemical conversion treated steel sheet and method for producing the same
TW201527451A (en) Surface-treated agent for metal material, surface-treated metal material and method for producing same

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 16783125

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2017514114

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 16783125

Country of ref document: EP

Kind code of ref document: A1