WO2019155858A1 - 絶縁被膜付き電磁鋼板およびその製造方法 - Google Patents

絶縁被膜付き電磁鋼板およびその製造方法 Download PDF

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WO2019155858A1
WO2019155858A1 PCT/JP2019/001690 JP2019001690W WO2019155858A1 WO 2019155858 A1 WO2019155858 A1 WO 2019155858A1 JP 2019001690 W JP2019001690 W JP 2019001690W WO 2019155858 A1 WO2019155858 A1 WO 2019155858A1
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Prior art keywords
insulating
coating layer
tension
steel sheet
coating
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PCT/JP2019/001690
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English (en)
French (fr)
Inventor
敬 寺島
聖啓 末宗
花梨 國府
俊人 ▲高▼宮
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Ｊｆｅスチール株式会社
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Application filed by Ｊｆｅスチール株式会社 filed Critical Ｊｆｅスチール株式会社
Priority to US16/967,945 priority Critical patent/US11923115B2/en
Priority to JP2019524295A priority patent/JP7016358B2/ja
Priority to CN201980012105.XA priority patent/CN111684106B/zh
Priority to KR1020207022636A priority patent/KR102483593B1/ko
Priority to RU2020126233A priority patent/RU2749507C1/ru
Priority to EP19751911.9A priority patent/EP3722460A4/en
Publication of WO2019155858A1 publication Critical patent/WO2019155858A1/ja

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    • 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
    • C23C24/00—Coating starting from inorganic powder
    • C23C24/08—Coating starting from inorganic powder by application of heat or pressure and heat
    • 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
    • C23C24/00—Coating starting from inorganic powder
    • C23C24/08—Coating starting from inorganic powder by application of heat or pressure and heat
    • C23C24/082—Coating starting from inorganic powder by application of heat or pressure and heat without intermediate formation of a liquid in the layer
    • 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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/04—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material
    • 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
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
    • C23G1/08—Iron or steel
    • C23G1/083—Iron or steel solutions containing H3PO4
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
    • H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
    • H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
    • H01F1/12—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials
    • H01F1/14—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials metals or alloys
    • H01F1/147—Alloys characterised by their composition
    • 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
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C2202/00—Physical properties
    • C22C2202/02—Magnetic
    • 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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
    • C23C18/1208—Oxides, e.g. ceramics
    • C23C18/1212—Zeolites, glasses
    • 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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/1229—Composition of the substrate
    • C23C18/1241—Metallic substrates
    • 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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/125—Process of deposition of the inorganic material
    • C23C18/1262—Process of deposition of the inorganic material involving particles, e.g. carbon nanotubes [CNT], flakes
    • C23C18/127—Preformed particles

Definitions

  • the present invention relates to an electromagnetic steel sheet with an insulating coating and a method for producing the same.
  • the present invention relates to an electrical steel sheet with an insulating coating that has excellent coating adhesion of the insulating coating and has a high coating tension, and more particularly to a grain-oriented electrical steel sheet with an insulating coating.
  • Electromagnetic steel sheets are soft magnetic materials that are widely used as iron core materials for rotating machines and stationary machines.
  • grain-oriented electrical steel sheets are soft magnetic materials used as core materials for transformers and generators, and have a crystal structure in which the ⁇ 001> orientation, which is the easy axis of iron, is highly aligned with the rolling direction of the steel sheet. It is.
  • Such a texture preferentially grows crystal grains with a (110) [001] orientation, which is called a Goss orientation, during secondary recrystallization annealing during the production process of grain-oriented electrical steel sheets. Formed through secondary recrystallization.
  • a grain-oriented electrical steel sheet has two layers of insulation: a layer mainly composed of forsterite (forsterite film layer) and a layer mainly composed of silicate glass (insulation tension film layer) from the side in contact with the steel sheet.
  • a coating is applied.
  • Silicate glass coating has the purpose of imparting insulation, workability, rust prevention, etc., but glass and metal have low adhesion, so the ceramic layer mainly composed of forsterite is made of insulating tension coating layer and steel plate. It is common to form between.
  • the insulating film having such a structure is formed at a high temperature, and has a low coefficient of thermal expansion compared to the steel sheet, so that a tension is applied to the steel sheet due to the difference in the coefficient of thermal expansion between the steel sheet and the insulating film when the temperature decreases to room temperature.
  • a tension is applied to the steel sheet due to the difference in the coefficient of thermal expansion between the steel sheet and the insulating film when the temperature decreases to room temperature.
  • Patent Document 2 has a film mainly composed of magnesium phosphate, colloidal silica and chromic anhydride
  • Patent Document 3 has a film mainly composed of aluminum phosphate, colloidal silica and chromic anhydride.
  • Patent Document 4 discloses a technique for preventing seizure at the time of strain relief annealing and preventing deterioration of film adhesion.
  • Patent Document 5 discloses a technique for crystallizing glass as a technique for forming a higher-tensile film and improving magnetic properties.
  • JP-A-8-67913 Japanese Patent Laid-Open No. 50-79442 JP 48-39338 A Japanese Unexamined Patent Publication No. 63-111604 JP 2007-217758 A
  • An object of the present invention is to provide an electrical steel sheet with an insulating coating excellent in coating adhesion of the insulating coating and a method for producing the same.
  • the inventors bent the grain-oriented electrical steel sheet on which an insulating film with increased tension was formed by using crystallization, and investigated in detail the site where the film was peeled off. It was also found that it occurred at the interface between the insulating tension coating layer A) and the forsterite coating layer (hereinafter also referred to as insulating coating layer B). As a result of intensive investigations on the method for preventing film peeling based on the results of this investigation, the shear stress generated at the interface between the insulating tension coating layer A and the insulating coating layer B (hereinafter referred to as the coating layer A / B interface) is reduced. It was found that peeling can be avoided.
  • the distribution of the crystallized phase in the insulating tension coating layer A is made to have a super low thermal expansion on the surface layer side and a low thermal expansion on the coating layer A / B interface side as low as the conventional coating by forming a concentration gradient in the coating thickness direction
  • the present invention was completed successfully.
  • the present invention has the following configuration.
  • the insulation tension coating layer A contains one or more elements selected from Mg, Al, Ca, Ba, Sr, Zn, Ti, Nd, Mo, Cr, B, Ta, Cu, and Mn.
  • the insulating tension The coating layer A includes at least one selected from salts of phosphoric acid, boric acid and silicic acid Mg, Al, Ca, Ba, Sr, Zn, Ti, Nd, Mo, Cr, Ta, Cu, and Mn. And a coating forming treatment liquid containing colloidal silica is applied to at least one surface of the magnetic steel sheet, and after the coating, a temperature range of 600 ° C. to 700 ° C.
  • the insulating tension The coating layer A is made of at least one selected from Mg, Al, Ca, Ba, Sr, Zn, Cr and Mn salts of phosphoric acid, colloidal silica, Ti, Nd, Mo, B, Ta,
  • a film-forming treatment liquid containing one or two or more compounds selected from Cu is applied to at least one surface of a magnetic steel sheet, and after the application, a temperature range of 600 ° C. or more and 700 ° C. or less.
  • an electrical steel sheet with an insulating coating excellent in coating adhesion of the insulating coating can be obtained.
  • an electrical steel sheet with an insulating coating having excellent coating adhesion of the insulating coating and a high coating tension can be obtained.
  • the tension applied to the steel sheet by the insulating coating can be increased, and when the wound core is processed, the coating adhesion at the innermost winding portion is improved.
  • An insulating steel sheet with an insulating coating is also obtained.
  • a sample was manufactured as follows. Thickness: 0.23 mm finished annealed grain-oriented electrical steel sheet is sheared to a size of 300 mm ⁇ 100 mm to remove unreacted annealing separator, and then subjected to strain relief annealing (800 ° C. 2 hours, N 2 atmosphere). A film (insulating film layer B) mainly composed of forsterite was formed on the surface of the steel sheet after strain relief annealing. Next, it pickled lightly with 5 mass% phosphoric acid aqueous solution. Then, the insulating film was formed as follows with respect to the steel plate after the said light pickling.
  • the insulating tension coating layer A was formed on the insulating coating layer B (forsterite coating) by baking under the conditions of%, water vapor dew point: ⁇ 10 ° C.
  • the distribution of the tension applied to the steel sheet by the insulation tension coating layer A in the insulation tension coating layer A is removed by removing the insulation tension coating layer A from one side of the sample at various removal rates. It was determined by measuring the peeled amount of the applied insulating tension coating layer A and the applied tension at that time.
  • As a method for removing the insulation tension coating layer A only from one side of the sample with various removal rates masking with an adhesive tape so that the insulation coating on the other side is not removed, and then 110 ° C., 25 mass% NaOH. It was performed by adjusting the time of immersion in the aqueous solution.
  • the amount of peeling (g / m 2 ) of the insulation tension coating layer A was calculated from the difference in mass (g) of the sample before and after peeling of the coating and the surface area (m 2 ) of one side of the sample.
  • the tension applied to the steel sheet is the tension in the rolling direction, and a test piece (rolling direction 280 mm ⁇ rolling perpendicular direction 30 mm) prepared from a sample from which the insulation tension coating layer A has been removed from the one side at various removal rates is fixed at one end. Then, the amount of warpage was measured using a test piece of 250 mm as a measurement length, and calculated using the following formula (I).
  • the adhesiveness of the insulating coating of each sample is not poor when the test material having a rolling direction of 280 mm ⁇ the rolling perpendicular direction of 30 mm is wound around a round bar having a diameter of 10 mm and bent back by 180 °. Things were good.
  • Table 1 shows the amount of peeling of the insulating tension coating layer A and the applied tension measured at that time. Moreover, the evaluation result of the film adhesion of each sample is also described.
  • the applied tension when the peel amount of the insulating tension coating layer A is 0.50 g / m 2 is 1.4 MPa in Conventional Example 1, 0.9 MPa in Conventional Example 2, and 3. It was 8 MPa.
  • M is equivalent to the tension applied to the steel sheet by the insulating tension coating layer having a basis weight of M / 9 from the surface).
  • the peeling amount of the insulating tension coating layer A is 1.00, 1.50, 2.00, 2.25, 3.00, 4.50 g / m 2
  • the peeling amount of the insulating tension coating layer A is as follows. The same view as when 0.50 g / m 2 can be obtained.
  • the applied tension when the peel amount of the insulation tension coating layer A is 2.25 g / m 2 is 5.3 MPa in Conventional Example 1, 3.9 MPa in Conventional Example 2, and 10.5 MPa in Invention Example.
  • the tension applied to the steel sheet by the insulating tension coating layer having a basis weight of 2.25 g / m 2 from the surface of the insulating tension coating layer A corresponds to the tension applied to the steel sheet by the insulating tension coating layer having a basis weight M / 2 from the surface).
  • the applied tension when the peel amount of the insulation tension coating layer A is 4.50 g / m 2 is 10.5 MPa in Conventional Example 1, 7.8 MPa in Conventional Example 2, and 11.3 MPa in Invention Example.
  • FIG. 1 shows the data in Table 1 above, with the peel amount of the insulating tension coating layer A on the horizontal axis, and the applied tension at the peel amount on the vertical axis, Invention Example, Conventional Example 1, Conventional Example 2, Invention Example. About each example of these, the relationship between the peeling amount of the insulation tension
  • the applied tension is inclined in the insulating tension coating layer A, and the distribution of the applied tension in the insulating tension coating layer A is greatly different from the conventional example. Recognize. That is, in the conventional example, the peeling amount of the insulating tension coating layer A and the applied tension are approximately proportional to each other, whereas in the invention example, the peeling amount of the insulating tension coating layer A and the applied tension are not proportional to each other.
  • the applied tension in the film thickness direction of the tension coating layer A is biased.
  • the insulating tension coating layer A as a whole is 11.3 MPa and the conventional example (conventional example 1: 10.5 MPa, conventional example 2: It can be seen that the tension is better than (7.8 MPa) and the film adhesion is also good.
  • the electromagnetic steel sheet used in the present invention can be either a directional electromagnetic steel sheet or a non-oriented electrical steel sheet manufactured by a known method.
  • the grain-oriented electrical steel sheet is preferably manufactured by the following method.
  • % which is a unit of content of each element, means mass%.
  • C 0.001 to 0.10%
  • C is a component useful for the generation of goth-oriented crystal grains, and in order to effectively exhibit such action, it is preferable to contain 0.001% or more of C.
  • the C content is preferably in the range of 0.001 to 0.10%.
  • Si 1.0-5.0%
  • Si is a component necessary for increasing the electrical resistance to lower the iron loss and stabilizing the iron BCC structure to enable high-temperature heat treatment, and is preferably contained at least 1.0%.
  • the Si content is preferably in the range of 1.0 to 5.0%.
  • the Si content is more preferably in the range of 2.0 to 5.0%.
  • Mn 0.01 to 1.0% Mn not only effectively contributes to the improvement of hot brittleness of steel, but when S and Se are mixed, precipitates such as MnS and MnSe are formed and function as a grain growth inhibitor. To demonstrate. When the content of Mn is less than 0.01%, the above effect is insufficient. On the other hand, when the content exceeds 1.0%, the particle size of precipitates such as MnSe is coarsened and the effect as an inhibitor may be lost. There is. Therefore, the Mn content is preferably in the range of 0.01 to 1.0%.
  • Al 0.003 to 0.050%
  • Al is a useful component that forms an AlN in the steel and acts as an inhibitor as a dispersed second phase, but if the addition amount is less than 0.003%, a sufficient precipitation amount may not be secured, If added over 0.050%, AlN may precipitate coarsely and lose its action as an inhibitor. Therefore, the Al content is sol.
  • Al is preferably in the range of 0.003 to 0.050%.
  • N 0.001 to 0.020%
  • N is a component necessary for forming AlN as well as Al. If the amount added is less than 0.001%, the precipitation of AlN may be insufficient, and if it exceeds 0.020%, blistering or the like may occur during slab heating. Therefore, the N content is preferably in the range of 0.001 to 0.020%.
  • Total of one or two selected from S and Se 0.001 to 0.05%
  • S or Se is a useful component that combines with Mn or Cu to form MnSe, MnS, Cu 2 -xSe, Cu 2 -xS, and exerts an inhibitor action as a dispersed second phase in steel. If the total content of S and Se is less than 0.001%, the effect of addition is poor. On the other hand, if it exceeds 0.05%, not only is the solid solution during slab heating incomplete, May cause surface defects. For this reason, the content of one or two selected from S and Se is 0.001 to 0.05% in total in the case of adding S or Se alone or in combination (using both S and Se). The range of is preferable.
  • the above as the basic components of steel. Further, the balance other than the above can be composed of Fe and inevitable impurities.
  • B 0.001 to 0.01%
  • Ge 0.001 to 0.1%
  • P 0.005 to 0.1 %
  • Te 0.005 to 0.1%
  • Nb 0.005 to 0.1%
  • Ti 0.005 to 0.1%
  • V 0.005 to 0.1%
  • Or 2 or more types can be added to steel. By adding one or two or more of these, the crystal grain growth suppressing power is further strengthened, and a higher magnetic flux density can be stably obtained.
  • the steel having the composition described above is melted by a conventionally known refining process to form a steel material (steel slab) using a continuous casting method or ingot-bundling rolling method, and then the steel slab is heated. It is hot-rolled by hot rolling, and is subjected to hot-rolled sheet annealing as necessary, and then cold-rolled at the final thickness by one or more cold rollings sandwiching intermediate annealing. Then, after performing primary recrystallization annealing and decarburization annealing, an annealing separator containing MgO as a main component is applied and final finish annealing is performed, and the insulating coating layer B is a coating layer mainly composed of forsterite (forsterite).
  • the electrical steel sheet with the insulating coating can be manufactured by a manufacturing method comprising a series of steps of forming the insulating tension coating layer (insulating tension coating layer A).
  • insulating tension coating layer A insulating tension coating layer A
  • insulating tension coating layer A insulating tension coating layer A
  • Insulating tension coating layer such as a ceramic layer having a different thermal expansion coefficient in the film thickness direction and a ceramic layer whose composition changes continuously.
  • Insulating tension coating layer A such as a ceramic layer having a different thermal expansion coefficient in the film thickness direction and a ceramic layer whose composition changes continuously.
  • the insulating tension coating layer A formed in this way is excellent in adhesion to the ground iron, the insulating tension coating layer A is directly formed on the surface of the ground iron without forming the base coating layer as described above. be able to.
  • the insulating tension coating layer A according to the present invention has an inclination in the applied tension in the film thickness direction in the insulating tension coating layer A.
  • the electrical steel sheet with an insulating coating of the present invention includes an insulating coating including the insulating tension coating layer A on the surface of the electrical steel sheet.
  • the insulating coating may be composed only of the insulating tension coating layer A, or a base coating such as a forsterite coating layer may be provided between the insulating tension coating layer A and the steel plate.
  • the electrical steel sheet with an insulating coating of the present invention may be used as a product as it is, or may be further provided with a coating formed by applying varnish or the like thereon.
  • the film formed by applying the above-described base film or varnish or the like does not have an inclination in the applied tension in the film thickness direction like the insulating tension film layer A of the present invention.
  • the electrical steel sheet with an insulating coating according to the present invention has an insulating coating including the insulating tension coating layer A formed on at least one surface of the electrical steel sheet.
  • the insulation coating layer having a basis weight M / 2 from the surface of the insulation tension coating layer A The tension applied to the steel plate is 0.80 ⁇ ⁇ A or more.
  • tensile_strength coating layer A provides with respect to a steel plate shall be the tension
  • the insulating tension coating layer A on the other side is removed using alkali, acid, etc., and then one end 30 mm of the test piece is fixed, and the portion of the test piece 250 mm is used as the measurement length.
  • the amount of warpage is measured and calculated using the following formula (I).
  • the insulation tension coating layer A is removed from one surface of the test piece at various removal rates, and the applied tension at that time is measured, whereby the insulation tension coating layer of the tension applied to the steel sheet by the insulation tension coating layer A is measured.
  • the distribution in A can be obtained.
  • the removal rate is immersed in the stripping solution on one side of the test piece (eg, 110 ° C., time for immersion in a 25% by weight NaOH aqueous solution). It can be adjusted arbitrarily by adjusting.
  • the tension applied to the steel sheet by the insulating tension coating layer having a weight per unit area M / 3 from the surface of the insulating tension coating layer A and the measurement was performed by peeling off the insulating tension coating layer having a basis weight of M / 2.
  • the applied tension corresponds to the tension applied to the steel sheet by the insulating coating layer having a basis weight M / 2 from the surface of the insulating tension coating layer A.
  • the weight per unit area of M that is, the applied tension when the insulation tension coating layer A was completely peeled from one side of the test piece and measured was equivalent to the tension ⁇ A applied to the steel plate by the entire insulation tension coating layer A.
  • the basis weight M (g / m 2 ) can be calculated from the mass difference (g) before and after peeling of the insulating tension coating layer A and the single-sided surface area (m 2 ) of the steel sheet.
  • the basis weight of the insulating tension coating layer A is M and the tension applied to the steel sheet by the insulating tension coating layer A is ⁇ A
  • the basis weight M / 2 of the insulating tension coating layer A is from the surface.
  • the tension ( ⁇ A / 2 ) applied to the steel sheet by the insulating tension coating layer needs to be 0.80 times or more of ⁇ A.
  • ⁇ A / 2 is less than 0.80 times, since the tension ( ⁇ A ⁇ A / 2 ) applied to the steel plate side half of the insulating tension coating layer A is still high, the coating interface (insulating tension coating layer) The shear stress at the interface between A and the undercoat such as forsterite coating layer or the interface between the insulation tension coating layer A and the ground iron becomes large, and the coating tends to peel off during bending, resulting in poor adhesion. End up. More preferably, ⁇ A / 2 is 0.85 times or more of ⁇ A.
  • ⁇ A / 2 is not particularly problematic up to 1.00 times as large as ⁇ A , but it can be realized considering the difference between the thermal expansion coefficient of the metal and the thermal expansion coefficient of the non-metal insulating coating.
  • ⁇ A / 2 is considered to be about 0.98 times ⁇ A.
  • the tension ( ⁇ A / 3 ) applied to the steel plate by the insulating tension coating layer having a basis weight M / 3 from the surface of the insulating tension coating layer A is preferably 0.50 times or more of ⁇ A , and More preferably, it is 60 times or more.
  • any material of nitride, sulfide, oxide, inorganic or organic matter can be used as long as it is a substance that ensures electrical insulation and imparts tension.
  • CVD or PVD method Al, Cr, Ti, V, Mn, Nb, Hf, Ta, W and their nitrides, oxides, oxynitrides, carbonitrides, etc. can be formed relatively easily. can do.
  • the insulating tension coating layer A is preferably composed mainly of oxides, preferably inorganic oxides, particularly composed mainly of glass or glass ceramics. Is preferred.
  • the main component means that the proportion contained in the insulating tension coating layer A is 50% by mass or more with respect to the total mass of the insulating tension coating layer A.
  • Silicate phosphate glass has the property of absorbing moisture in the atmosphere, so Mg, Al, Ca, Ba, Sr, Zn, Ti, Nd, Mo, Cr, B, Ta, Cu and Mn are used for the purpose of preventing this. It is preferable to contain one or more elements selected from among them. Moreover, you may contain arbitrary elements in addition to the said element. For example, in order to improve the smoothness of the surface, it is preferable to contain one or more elements selected from Li and K.
  • the insulating tension coating layer A is formed of a plurality of silicate glass layers having different applied tensions. Is mentioned. In this case, the insulating tension coating layer A is formed mainly of glass.
  • the simplest method for inclining the tension applied to the steel sheet in the insulation tension coating layer A is to deposit ceramic phases having different thermal expansion coefficients in the glassy tension coating (that is, mainly glass ceramics). In this case, the distribution of the ceramic phase is controlled.
  • a control method a method of depositing a ceramic phase having a large thermal expansion coefficient on the steel plate side of the insulating tension coating layer A or a method of depositing a low thermal expansion ceramic phase on the surface layer side of the insulating tension coating layer A can be considered.
  • a method of precipitating a low thermal expansion ceramic phase on the surface layer side is preferable.
  • Glass crystallization may occur from within the glass or from the glass surface. In the case of the present invention, it is most preferable to adopt a method in which crystallization is caused from the glass surface and this is grown inside the glass (that is, the steel plate side).
  • the film forming treatment liquid containing at least one selected from salts of Cr, Ta, Cu, and Mn and colloidal silica is applied to at least one surface of the electrical steel sheet.
  • the method of baking by the method of this is mentioned.
  • the film forming treatment liquid further includes at least one selected from phosphoric acid, boric acid, and silicic acid, for example, phosphoric acid, boric acid, and silicic acid Li, K salts.
  • an arbitrary compound for example, a compound containing one or more selected from Li, K, and Mg can be added to the film forming treatment liquid.
  • the arbitrary compound is preferably an inorganic compound.
  • At least one selected from salts of phosphoric acid Mg, Al, Ca, Ba, Sr, Zn, Cr, Mn, colloidal silica is applied to at least one surface of the electrical steel sheet, and after the application
  • tensile_strength film layer which has a silicate glass ceramic as a main body is mentioned.
  • the compound is preferably an inorganic compound.
  • an arbitrary compound for example, a compound containing one or more selected from Li, K, and Mg can be added to the film forming treatment liquid.
  • the arbitrary compound is preferably an inorganic compound.
  • the baking temperature of the insulating tension coating layer A is preferably 800 ° C. or higher and more preferably higher when crystallization is caused during baking. However, if the temperature becomes too high, the steel sheet itself undergoes creep deformation during baking, so the baking temperature is preferably 1100 ° C. or lower, and more preferably 1050 ° C. or lower. In order to cause crystallization at 800 ° C. or higher, it is necessary to adjust the composition of the coating liquid (film forming treatment liquid) so that the crystal nucleation temperature is about 600 ° C. to 700 ° C.
  • the temperature range from 600 ° C. to 700 ° C. to a heating rate of 100 ° C./second or more. More preferably, it is 150 ° C./second or more.
  • the upper limit of the heating rate in the temperature range of 600 ° C. or more and 700 ° C. or less is not particularly limited, but is practically preferably 400 ° C./second or less, more preferably 300 ° C./second or less.
  • the atmosphere in the temperature region of 700 ° C. or higher is preferably an atmosphere having a water vapor dew point of ⁇ 20 ° C. or higher.
  • An atmosphere having a water vapor dew point of ⁇ 15 ° C. or higher is preferred.
  • the atmosphere is below °C.
  • the insulation tension coating layer A having a gradient in the applied tension to the steel plate for example, PVD method or CVD method, Al, Cr, Ti, V, Mn, Nb, Hf, Ta, A method or ceramic layer in which W and these nitrides, oxides, oxynitrides, carbonitrides are formed while changing the composition and concentration in the film thickness direction, and ceramics having different thermal expansion coefficients are made into a layer structure Among them, a method of continuously changing the composition can be mentioned. Since the ceramic layer (insulating tension coating layer A) formed in this way is excellent in adhesion to the base iron, the insulating tension coating layer A is directly formed on the surface of the base iron without forming the base coating layer. be able to.
  • the tension applied to the steel sheet by the insulating tension coating layer A is preferably 10 MPa or more, and more preferably 12 MPa or more. This is because by increasing the tension, it is possible to reduce iron loss and further reduce noise when a transformer is used.
  • the basis weight of the insulating tension coating layer A is preferably 2.0 g / m 2 or more on one side. Further, the basis weight of the insulating tension coating layer A is preferably 12.0 g / m 2 or less on one side. When the basis weight is less than 2.0 g / m 2 , the interlayer insulation is slightly lowered. On the other hand, when the basis weight is more than 12.0 g / m 2 , the space factor decreases.
  • the space factor is a value defined by JIS C 2550. More preferably, the basis weight of the insulating tension coating layer A is 3.0 g / m 2 or more on one side. More preferably, the basis weight of the insulating tension coating layer A is 8.0 g / m 2 or less on one side.
  • Example 1 In mass%, Si: 3.25%, C: 0.04%, Mn: 0.08%, S: 0.002%, sol.
  • a silicon steel sheet slab containing Al: 0.015%, N: 0.006%, Cu: 0.05%, Sb: 0.01% is heated at 1150 ° C. for 20 minutes and then hot-rolled to 2.4 mm. After hot annealing at 1000 ° C. for 1 minute, a final plate thickness of 0.27 mm was obtained by cold rolling, and a 100 mm ⁇ 400 mm size was obtained from the center of the obtained cold rolled coil. The sample was collected, heated from room temperature to 820 ° C.
  • an annealing separator obtained by mixing 5 parts by mass of TiO 2 with respect to 100 parts by mass of MgO was applied to a water slurry and then dried.
  • the steel sheet is heated from 300 ° C. to 800 ° C. over 100 hours, and then heated to 1200 ° C. at 50 ° C./hr, and annealed at 1200 ° C. for 5 hours to perform forsterite as a main component.
  • a steel plate with an undercoat was prepared.
  • a coating solution for forming a film described in Table 2 was prepared, and an insulating tension film (insulating tension film layer A) was formed under the baking conditions described in Table 3. That is, in this example, the insulating tension coating layer A is formed on the forsterite base coating layer.
  • the specific gravity of the coating solution was adjusted to 1.20 using pure water.
  • the treatment liquid was applied using a roll coater, and the basis weight of each insulation tension coating layer A was 4.50 g / m 2 on one side.
  • the baking atmosphere was N 2 : 100% atmosphere, and the atmospheric dew point (water vapor dew point) in the temperature range of 700 ° C. or higher was as shown in Table 3.
  • the distribution of the tension applied to the steel sheet by the insulating tension coating layer A in the insulating tension coating layer A was measured by the method described above.
  • the peeling amount of the insulation tension coating layer A was adjusted by adjusting the time of dipping in an aqueous NaOH solution (stripping solution) of 110 ° C. and 25% by mass.
  • the adhesiveness of the insulating coating was evaluated by a round bar winding method. Specifically, when a test piece (rolling direction: 280 mm ⁇ rolling perpendicular direction: 30 mm) was wound around a round bar having a diameter of 5 mm and bent back by 180 °, the presence or absence of film peeling was examined visually.
  • Table 3 as described in, sigma A / 2 is in the present invention is more 0.80 times the ⁇ A ( ⁇ A / 2 / ⁇ A is 0.80 or higher), a bending peel diameter and excellent 15mm or less coating Adhesion. Furthermore, it can be seen that when ⁇ A / 2 is 0.85 times or more of ⁇ A , the bending peel diameter is 5 mm or less, and the coating adhesion is even better. Under the influence of the baking conditions, if the heating rate in the temperature range of 600 ° C. or higher and 700 ° C. or lower is 100 ° C./s or higher and the baking temperature is 800 ° C. or higher, ⁇ A / 2 / ⁇ A is 0.80 or higher. It can be seen that an insulating coating can be obtained.
  • Example 2 In mass%, Si: 3.25%, C: 0.04%, Mn: 0.08%, S: 0.002%, sol.
  • a silicon steel sheet slab containing Al: 0.015%, N: 0.006%, Cu: 0.05%, Sb: 0.01% is heated at 1150 ° C for 20 minutes and then hot-rolled to 2.2 mm. After hot annealing at 1000 ° C for 1 minute, it was cold rolled to a final thickness of 0.23 mm and subsequently increased from room temperature to 820 ° C at a heating rate of 50 ° C / s.
  • a primary recrystallization annealing was performed at 820 ° C. for 60 seconds in a warm and humid atmosphere.
  • an annealing separator obtained by mixing 150 parts by mass of Al 2 O 3 and 1 part by mass of Na 2 B 4 O 7 ⁇ 10H 2 O with respect to 50 parts by mass of MgO was applied to a water slurry and then dried.
  • the steel sheet is heated from 300 ° C. to 800 ° C. over 100 hours, and then heated to 1200 ° C. at 50 ° C./hr and annealed at 1200 ° C. for 5 hours to perform cordierite (2MgO ⁇
  • a steel plate having a crystalline coating mainly composed of 2Al 2 O 3 ⁇ 5SiO 2 was prepared.
  • the cordierite film is peeled off from the steel sheet (rolling direction: 400 mm x rolling direction: 100 mm) with a mixed acid of sulfuric acid and hydrofluoric acid.
  • the PVD method is used to make the steel sheet surface 100% TiN and the surface side 100% AlN on the steel sheet surface.
  • the insulation tension film (insulation tension film layer A) which made the middle the continuous solid solution of AlTiN was formed. That is, in this example, the insulating tension coating layer A is directly formed on the surface of the ground iron.
  • samples having insulating coatings having various concentration gradients (Al / Ti ratio) were prepared by changing the timing of turning on / off the bias voltage of the Ti target and Al target. Specifically, No. 4 in Table 4 is used.
  • the timing when the bias voltage of the Ti target was turned ON was set to 0 seconds, the voltage was applied to the Ti target from 0 seconds to 400 seconds, and the bias voltage of the Ti target was turned ON to the Al target.
  • a voltage is applied 300 seconds after the timing, and a voltage is applied from 300 seconds to 600 seconds to form the insulating tension coating layer A, thereby forming an insulating coating having a concentration gradient (Al / Ti ratio) in the insulating tension coating layer A. Formed.
  • the film has excellent coating adhesion with a bending peel diameter of 10 mm or less. Furthermore, it can be seen that when ⁇ A / 2 / ⁇ A is 0.85 or more, the bending peel diameter is 5 mm or less, and the coating adhesion is even better.

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Abstract

絶縁被膜の被膜密着性に優れる絶縁被膜付き電磁鋼板およびその製造方法を提供すること。　絶縁張力被膜層Ａを含む絶縁被膜を少なくとも片面に有する絶縁被膜付き電磁鋼板であって、前記絶縁張力被膜層Ａの目付量をＭ、前記絶縁張力被膜層Ａが鋼板に対して与える張力をσＡとしたとき、前記絶縁張力被膜層Ａのうち表面から目付量Ｍ／２の絶縁張力被膜層が鋼板に与える張力が０．８０×σＡ以上である絶縁被膜付き電磁鋼板。前記絶縁張力被膜層Ａを、リン酸、ホウ酸およびケイ酸のＭｇ、Ａｌ、Ｃａ、Ｂａ、Ｓｒ、Ｚｎ、Ｔｉ、Ｎｄ、Ｍｏ、Ｃｒ、Ｔａ、Ｃｕ、Ｍｎの塩のうちから選ばれる少なくとも１種と、コロイド状シリカと、を含む被膜形成用処理液を、電磁鋼板の少なくとも一方の表面に塗布し、前記塗布後、６００℃以上７００℃以下の温度域を１００℃／秒以上の加熱速度で加熱したのち、８００℃以上で焼付けて形成する絶縁被膜付き電磁鋼板の製造方法。

Description

絶縁被膜付き電磁鋼板およびその製造方法
　本発明は、絶縁被膜付き電磁鋼板およびその製造方法に関する。なかでも本発明は、絶縁被膜の被膜密着性に優れ、かつ、被膜張力が大きい絶縁被膜付き電磁鋼板に関し、特に絶縁被膜付き方向性電磁鋼板に関するものである。
　電磁鋼板は、回転機、静止器の鉄心材料として広く利用されている軟磁性材料である。特に、方向性電磁鋼板は、変圧器や発電機の鉄心材料として用いられる軟磁性材料で、鉄の磁化容易軸である＜００１＞方位が鋼板の圧延方向に高度に揃った結晶組織を有するものである。このような集合組織は、方向性電磁鋼板の製造工程中、二次再結晶焼鈍の際にいわゆるゴス（Ｇｏｓｓ）方位と称される（１１０）〔００１〕方位の結晶粒を優先的に巨大成長させる、二次再結晶を通じて形成される。
　一般に、方向性電磁鋼板には、鋼板と接する側からフォルステライトを主体とする層（フォルステライト被膜層）、珪リン酸塩ガラスを主体とする層（絶縁張力被膜層）の２層からなる絶縁被膜が施されている。珪リン酸塩ガラス被膜は、絶縁性、加工性および防錆性等を付与する目的を持つが、ガラスと金属は密着性が低いためフォルステライトを主体とするセラミックス層を絶縁張力被膜層と鋼板の間に形成することが一般的である。かかる構成の絶縁被膜は高温で形成され、しかも鋼板と比較して低い熱膨張率を持つことから室温まで下がったときの鋼板と絶縁被膜との熱膨張率の差異により鋼板に張力が付与され、鉄損を低減させる効果がある。また、無方向性電磁鋼板においても圧縮応力による特性の劣化を緩和する目的で鋼板に引っ張り応力を与えることが好ましい。そのため電磁鋼板の分野、特に方向性電磁鋼板の分野においては、たとえば特許文献１のように８ＭＰａ以上とできるだけ高い張力を鋼板に付与することが望まれている。
　このような要望を満たすために、従来から種々のガラス質被膜が提案されている。例えば、特許文献２には、リン酸マグネシウム、コロイド状シリカおよび無水クロム酸を主体とする被膜が、また特許文献３には、リン酸アルミニウム、コロイド状シリカおよび無水クロム酸を主体とする被膜がそれぞれ提案されている。また特許文献４には、歪取焼鈍時の焼き付き防止と被膜密着性の劣化を防止する技術が開示されている。さらに、より高張力な被膜を形成し、磁気特性を向上させる技術として、特許文献５にはガラスを結晶化させる技術が開示されている。
特開平８－６７９１３号公報 特開昭５０－７９４４２号公報 特開昭４８－３９３３８号公報 特開昭６３－１１１６０４号公報 特開２００７－２１７７５８号公報
　適切な結晶相（つまり熱膨張係数が小さい結晶）を選択することにより、高張力な絶縁被膜を得ることができるようになり、磁気特性が向上するというメリットがある。一方、鋼板と絶縁被膜との熱膨張係数差が大きくなりすぎることによって、絶縁被膜と鋼板の界面もしくは絶縁張力被膜層とフォルステライト被膜層の界面に大きなせん断応力が生じ、特に巻コアを製造する際に最内巻部で被膜が剥離してしまうという問題が発生しやすくなることが分かった。
　本発明は、絶縁被膜の被膜密着性に優れる絶縁被膜付き電磁鋼板およびその製造方法を提供することを目的とする。
　発明者らは、結晶化を利用して張力を高めた絶縁被膜を形成した方向性電磁鋼板を曲げ加工し、被膜が剥離した部位を詳細に調査したところ、被膜剥離が絶縁張力被膜層（以下、絶縁張力被膜層Ａともいう）とフォルステライト被膜層（以下、絶縁被膜層Ｂともいう）の界面で生じていることを見出した。本調査結果に基づき被膜剥離を防止する方法を鋭意検討したところ、絶縁張力被膜層Ａと絶縁被膜層Ｂとの界面（以下、被膜層Ａ／Ｂ界面という）に生じるせん断応力を低減することで剥離を回避できることを見出した。その方法として、被膜層Ａ／Ｂ間に新たに中間層Ｃを挟む方法が考えられたが、この場合絶縁被膜形成のための工程が１つ増加するため、製造コスト面で不利であった。そこで発明者らは、絶縁被膜形成のための工程を増加させることなく被膜層Ａ／Ｂ界面のせん断応力を低減した状態で絶縁張力被膜層Ａによる鋼板への付与張力を高める手法を鋭意検討した結果、絶縁張力被膜層Ａ内の結晶化相の分布を、被膜厚み方向に濃度勾配を形成することによって表層側で超低熱膨張、被膜層Ａ／Ｂ界面側で従来被膜程度の低熱膨張とすることに成功し、本発明を完成させた。
　すなわち、本発明は以下の構成を備える。
［１］絶縁張力被膜層Ａを含む絶縁被膜を少なくとも片面に有する絶縁被膜付き電磁鋼板であって、前記絶縁張力被膜層Ａの目付量をＭ、前記絶縁張力被膜層Ａが鋼板に対して与える張力をσＡとしたとき、前記絶縁張力被膜層Ａのうち表面から目付量Ｍ／２の絶縁張力被膜層が鋼板に与える張力が０．８０×σＡ以上である絶縁被膜付き電磁鋼板。
［２］前記絶縁張力被膜層Ａが、ガラスまたはガラスセラミックスを主体とする［１］に記載の絶縁被膜付き電磁鋼板。
［３］前記絶縁張力被膜層Ａが、Ｍｇ、Ａｌ、Ｃａ、Ｂａ、Ｓｒ、Ｚｎ、Ｔｉ、Ｎｄ、Ｍｏ、Ｃｒ、Ｂ、Ｔａ、ＣｕおよびＭｎのうちから選ばれる１種以上の元素を含む珪リン酸塩ガラスまたは珪リン酸塩ガラスセラミックスである［１］または［２］に記載の絶縁被膜付き電磁鋼板。
［４］絶縁張力被膜層Ａを含む絶縁被膜を少なくとも片面に有する絶縁被膜付き電磁鋼板の製造方法であって、前記絶縁張力被膜層Ａの目付量をＭ、前記絶縁張力被膜層Ａが鋼板に対して与える張力をσＡとしたとき、前記絶縁張力被膜層Ａのうち表面から目付量Ｍ／２の絶縁張力被膜層が鋼板に与える張力が０．８０×σＡ以上であり、前記絶縁張力被膜層Ａを、リン酸、ホウ酸およびケイ酸のＭｇ、Ａｌ、Ｃａ、Ｂａ、Ｓｒ、Ｚｎ、Ｔｉ、Ｎｄ、Ｍｏ、Ｃｒ、Ｔａ、Ｃｕ、Ｍｎの塩のうちから選ばれる少なくとも１種と、コロイド状シリカと、を含む被膜形成用処理液を、電磁鋼板の少なくとも一方の表面に塗布し、前記塗布後、６００℃以上７００℃以下の温度域を１００℃／秒以上の加熱速度で加熱したのち、８００℃以上で焼付けて形成する、絶縁被膜付き電磁鋼板の製造方法。
［５］絶縁張力被膜層Ａを含む絶縁被膜を少なくとも片面に有する絶縁被膜付き電磁鋼板の製造方法であって、前記絶縁張力被膜層Ａの目付量をＭ、前記絶縁張力被膜層Ａが鋼板に対して与える張力をσＡとしたとき、前記絶縁張力被膜層Ａのうち表面から目付量Ｍ／２の絶縁張力被膜層が鋼板に与える張力が０．８０×σＡ以上であり、前記絶縁張力被膜層Ａを、リン酸のＭｇ、Ａｌ、Ｃａ、Ｂａ、Ｓｒ、Ｚｎ、Ｃｒ、Ｍｎの塩のうちから選ばれる少なくとも１種と、コロイド状シリカと、Ｔｉ、Ｎｄ、Ｍｏ、Ｂ、Ｔａ、Ｃｕのうちから選ばれる１種もしくは２種以上を含む化合物と、を含む被膜形成用処理液を、電磁鋼板の少なくとも一方の表面に塗布し、前記塗布後、６００℃以上７００℃以下の温度域を１００℃／秒以上の加熱速度で加熱したのち、８００℃以上で焼付けて形成する、絶縁被膜付き電磁鋼板の製造方法。
［６］７００℃以上の温度域での雰囲気を、水蒸気露点：－２０℃以上１０℃以下の雰囲気とする［４］または［５］に記載の絶縁被膜付き電磁鋼板の製造方法
　本発明によれば、絶縁被膜の被膜密着性に優れる絶縁被膜付き電磁鋼板が得られる。
　本発明によれば、絶縁被膜の被膜密着性に優れ、かつ、被膜張力が大きい絶縁被膜付き電磁鋼板が得られる。本発明によれば、低熱膨張の絶縁張力被膜層を形成した際に、絶縁被膜が鋼板へ付与する張力を高くすることができ、巻コア加工した際に最内巻部での被膜密着性にも優れる絶縁被膜付き電磁鋼板が得られる。
従来例１、従来例２、発明例における絶縁張力被膜層Ａの剥離量と付与張力の関係を示すグラフである。
　以下、本発明の基礎となった実験結果について説明する。
　まず、試料を次のようにして製作した。
　公知の方法で製造された板厚：０．２３ｍｍの仕上焼鈍済みの方向性電磁鋼板を３００ｍｍ×１００ｍｍの大きさにせん断し、未反応の焼鈍分離剤を除去した後、歪取焼鈍（８００℃、２時間、Ｎ２雰囲気）を施した。歪取焼鈍後の前記鋼板の表面にはフォルステライトを主体とする被膜（絶縁被膜層Ｂ）が形成していた。次に、５質量％リン酸水溶液で軽酸洗した。その後、前記軽酸洗後の鋼板に対して、以下のようにして絶縁被膜を形成した。
（従来例１）特許文献５の本発明４の絶縁張力被膜を前記特許文献５に記載のとおり施し、絶縁被膜層Ｂ（フォルステライト被膜）の上に、前記絶縁張力被膜（絶縁張力被膜層Ａ）を形成した。
（従来例２）特許文献４の発明例である実施例１第２表のＮｏ．３の絶縁張力被膜を前記特許文献４に記載のとおり施し、絶縁被膜層Ｂ（フォルステライト被膜）の上に、前記絶縁張力被膜（絶縁張力被膜層Ａ）を形成した。
（発明例）第一リン酸マグネシウム水溶液を固形分換算で１００質量部、コロイド状シリカを固形分換算で５０質量部、硝酸マグネシウム６水和物を５０質量部混合した水溶液を純水で希釈して比重１．２０に調整した被膜形成用処理液を乾燥後目付け量が両面で９．００ｇ／ｍ２（片面で４．５０ｇ／ｍ２）となるようにロールコーターにて塗布した。次に、乾燥炉に装入し（３００℃、１分間）、その後、６００℃～７００℃の温度域を１５０℃／秒の加熱速度で加熱した後、８５０℃、３０秒間、Ｎ２：１００％、水蒸気露点：－１０℃の条件で焼付を実施して、絶縁被膜層Ｂ（フォルステライト被膜）の上に絶縁張力被膜層Ａを形成した。
　なお、従来例１、従来例２、発明例の試料とも、絶縁張力被膜層Ａの乾燥後目付量が片面で４．５０ｇ／ｍ２となるように調整した。
　かくして得られた試料について、絶縁張力被膜層Ａが鋼板に対して与える張力の絶縁張力被膜層Ａ中での分布を、試料の片面から種々の除去率で絶縁張力被膜層Ａを除去し、除去された絶縁張力被膜層Ａの剥離量と、その際の付与張力を測定することで求めた。試料の片面からのみ種々の除去率で絶縁張力被膜層Ａを除去する方法としては、もう一方の面の絶縁被膜が除去されないように粘着テープでマスキングしてから、１１０℃、２５質量％のＮａＯＨ水溶液に浸漬する時間を調整する方法で行った。
　絶縁張力被膜層Ａの剥離量（ｇ／ｍ２）は、被膜剥離前後の試料の質量差（ｇ）と試料の片面の表面積（ｍ２）より算出した。
　鋼板への付与張力は、圧延方向の張力とし、前記片面から種々の除去率で絶縁張力被膜層Ａを除去した試料から作成した試験片（圧延方向２８０ｍｍ×圧延直角方向３０ｍｍ）の片端３０ｍｍを固定して試験片２５０ｍｍの部分を測定長さとしてそり量を測定し、下記式（Ｉ）を用いて算出した。
鋼板への付与張力［ＭＰａ］＝鋼板ヤング率［ＧＰａ］×板厚［ｍｍ］×そり量［ｍｍ］÷（測定長さ［ｍｍ］）２×１０３・・・式（Ｉ）
ただし、鋼板ヤング率は、１３２ＧＰａとする。
　また、各試料の絶縁被膜の密着性は、圧延方向２８０ｍｍ×圧延直角方向３０ｍｍの試験材を、直径が１０ｍｍの丸棒に巻き付け、１８０°曲げ戻した際に被膜剥離のあるものを不良、ないものを良とした。
　表１に、絶縁張力被膜層Ａの剥離量と、その際に測定された付与張力を示す。また、各試料の被膜密着性の評価結果も併記する。
Figure JPOXMLDOC01-appb-T000001
  
　表１に示すように、絶縁張力被膜層Ａの剥離量が０．５０ｇ／ｍ２のときの付与張力は、従来例１で１．４ＭＰａ、従来例２で０．９ＭＰａ、発明例で３．８ＭＰａであった。これは、絶縁張力被膜層Ａのうち、表面から目付量０．５０ｇ／ｍ２の絶縁張力被膜層が鋼板に付与していた張力に相当する（すなわち絶縁張力被膜層Ａの片面の目付量をＭとした場合、表面から目付量Ｍ／９の絶縁張力被膜層が鋼板に対して付与していた張力に相当）。
　絶縁張力被膜層Ａの剥離量が１．００、１．５０、２．００、２．２５、３．００、４．５０ｇ／ｍ２のときについても、上記絶縁張力被膜層Ａの剥離量が０．５０ｇ／ｍ２のときと同様の見方ができる。
　例えば、絶縁張力被膜層Ａの剥離量が２．２５ｇ／ｍ２のときの付与張力は、従来例１で５．３ＭＰａ、従来例２で３．９ＭＰａ、発明例で１０．５ＭＰａであり、これは、絶縁張力被膜層Ａのうち、表面から目付量２．２５ｇ／ｍ２の絶縁張力被膜層が鋼板に付与していた張力に相当する（すなわち絶縁張力被膜層Ａの片面の目付量をＭとした場合、表面から目付量Ｍ／２の絶縁張力被膜層が鋼板に対して付与していた張力に相当）。
　また、絶縁張力被膜層Ａの剥離量が４．５０ｇ／ｍ２のときの付与張力は、従来例１で１０．５ＭＰａ、従来例２で７．８ＭＰａ、発明例で１１．３ＭＰａであり、これは、絶縁張力被膜層Ａのうち、表面から目付量４．５０ｇ／ｍ２の絶縁張力被膜層、すなわち絶縁張力被膜層Ａ全体が鋼板に付与していた張力に相当する。
　図１に、上記表１のデータを、絶縁張力被膜層Ａの剥離量を横軸に、前記剥離量のときの付与張力を縦軸にとり、発明例、従来例１、従来例２、発明例の各例について、絶縁張力被膜層Ａの剥離量と付与張力との関係を示す。
　表１、図１に示されるように、発明例では、絶縁張力被膜層Ａ中で付与張力に傾斜があり、絶縁張力被膜層Ａ中での付与張力の分布が、従来例と大きく異なることがわかる。すなわち、従来例では、絶縁張力被膜層Ａの剥離量と付与張力が概ね比例関係となるのに対し、発明例では、絶縁張力被膜層Ａの剥離量と付与張力が比例関係とならず、絶縁張力被膜層Ａの膜厚方向での付与張力に偏りがある。
　また、このように絶縁張力被膜層Ａ内で鋼板への付与張力に傾斜がある発明例では絶縁張力被膜層Ａ全体で１１．３ＭＰａと従来例（従来例１：１０．５ＭＰａ、従来例２：７．８ＭＰａ）よりも良好な張力を示すとともに、被膜密着性も良好であることがわかる。
　次に、本発明の各構成要件の限定理由について述べる。
　本発明に使用される電磁鋼板は公知の方法で製造される方向性電磁鋼板、無方向性電磁鋼板いずれでも使用することができる。方向性電磁鋼板は、一例として、次に示すような方法で製造されることが好ましい。
　まず、好ましい鋼の成分組成について説明する。以下、特に断らない限り、各元素の含有量の単位である％は質量％を意味する。
　Ｃ：０．００１～０．１０％
　Ｃはゴス方位結晶粒の発生に有用な成分であり、かかる作用を有効に発揮させるためには、０．００１％以上のＣを含有することが好ましい。一方、Ｃ含有量が０．１０％を超えると脱炭焼鈍によっても脱炭不良を起こすおそれがある。そのためＣ含有量は０．００１～０．１０％の範囲が好ましい。
　Ｓｉ：１．０～５．０％
　Ｓｉは、電気抵抗を高めて鉄損を低下させるとともに、鉄のＢＣＣ組織を安定化させて高温の熱処理を可能とするために必要な成分であり、少なくとも１．０％含有することが好ましい。一方、Ｓｉの含有量が５．０％を超えると冷間圧延が困難となるおそれがある。したがって、Ｓｉ含有量は１．０～５．０％の範囲が好ましい。Ｓｉ含有量は、２．０～５．０％の範囲がより好ましい。
　Ｍｎ：０．０１～１．０％
　Ｍｎは、鋼の熱間脆性の改善に有効に寄与するだけでなく、ＳやＳｅが混在している場合には、ＭｎＳやＭｎＳｅ等の析出物を形成し結晶粒成長の抑制剤としての機能を発揮する。Ｍｎの含有量が０．０１％より少ないと上記の効果が不十分であり、一方、１．０％を超えるとＭｎＳｅ等の析出物の粒径が粗大化してインヒビターとしての効果が失われるおそれがある。そのため、Ｍｎ含有量は０．０１～１．０％の範囲が好ましい。
　ｓｏｌ．Ａｌ：０．００３～０．０５０％
　Ａｌは、鋼中でＡｌＮを形成して分散第二相としてインヒビターの作用をする有用成分であるが、添加量が０．００３％に満たないと十分に析出量が確保できないおそれがあり、一方、０．０５０％を超えて添加するとＡｌＮが粗大に析出してインヒビターとしての作用が失われるおそれがある。そのため、Ａｌ含有量は、ｓｏｌ．Ａｌとして０．００３～０．０５０％の範囲が好ましい。
　Ｎ：０．００１～０．０２０％
　ＮもＡｌと同様にＡｌＮを形成するために必要な成分である。添加量が０．００１％を下回るとＡｌＮの析出が不十分となるおそれがあり、０．０２０％を超えて添加するとスラブ加熱時にふくれ等を生じるおそれがある。そのため、Ｎ含有量は０．００１～０．０２０％の範囲が好ましい。
　Ｓ及びＳｅのうちから選んだ１種又は２種の合計：０．００１～０．０５％
　Ｓ又はＳｅは、ＭｎやＣｕと結合してＭｎＳｅ、ＭｎＳ、Ｃｕ２－ｘＳｅ、Ｃｕ２－ｘＳを形成し鋼中の分散第二相としてインヒビターの作用を発揮する有用成分である。これらＳ、Ｓｅの合計の含有量が０．００１％に満たないとその添加効果に乏しく、一方、０．０５％を超える場合はスラブ加熱時の固溶が不完全となるだけでなく、製品表面の欠陥の原因ともなるおそれがある。そのため、Ｓ及びＳｅのうちから選んだ１種又は２種の含有量は、Ｓ又はＳｅの単独添加、複合添加（ＳとＳｅを併用）いずれの場合も合計で０．００１～０．０５％の範囲が好ましい。
　以上を鋼の基本成分とすることが好ましい。また、上記以外の残部は、Ｆｅおよび不可避的不純物の組成とすることができる。
　また、上記組成に、さらにＣｕ：０．０１～０．２％、Ｎｉ：０．０１～０．５％、Ｃｒ：０．０１～０．５％、Ｓｂ：０．０１～０．１％、Ｓｎ：０．０１～０．５％、Ｍｏ：０．０１～０．５％、Ｂｉ：０．００１～０．１％のうちから選ばれる１種以上添加することがきる。補助的なインヒビターとしての作用を有する元素を添加することでさらなる磁性向上が可能である。このような元素として、結晶粒径や表面に偏析しやすい上記の元素が上げられる。いずれも上記の添加量に満たない場合は、その効果が得られない。また、上記添加量を超えると被膜外観の不良や二次再結晶不良が発生しやすくなるので、上記範囲が好ましい。
　さらに、上記成分に加えて、Ｂ：０．００１～０．０１％、Ｇｅ：０．００１～０．１％、Ａｓ：０．００５～０．１％、Ｐ：０．００５～０．１％、Ｔｅ：０．００５～０．１％、Ｎｂ：０．００５～０．１％、Ｔｉ：０．００５～０．１％、Ｖ：０．００５～０．１％から選ばれる１種又は２種以上を鋼に添加することができる。これらの１種又は２種以上を添加することにより、結晶粒成長の抑制力がさらに強化されてより高い磁束密度を安定的に得ることができる。
　次に、絶縁被膜付き電磁鋼板の製造方法について説明する。
　上記に説明した成分組成を有する鋼を、従来公知の精錬プロセスで溶製し、連続鋳造法または造塊－分塊圧延法を用いて鋼素材（鋼スラブ）とし、その後、上記鋼スラブを熱間圧延して熱延板とし、必要に応じて熱延板焼鈍を施した後、１回もしくは中間焼鈍を挟む２回以上の冷間圧延を施して最終板厚の冷延板とする。その後、一次再結晶焼鈍と脱炭焼鈍を施した後、ＭｇＯを主成分とする焼鈍分離剤を塗布して最終仕上げ焼鈍を施し、絶縁被膜層Ｂとしてフォルステライトを主体とする被膜層（フォルステライト被膜層）を形成した後、絶縁張力被膜層（絶縁張力被膜層Ａ）を形成する一連の工程からなる製造方法で、絶縁被膜付き電磁鋼板を製造することが出来る。なお、前記のようにして製造した絶縁被膜付き電磁鋼板の表面に、ワニス等を塗布する等して適宜に被膜を設けてもよい。
　また、上記脱炭焼鈍後にＡｌ２Ｏ３などを主体とする焼鈍分離剤を塗布することにより最終仕上げ焼鈍後にフォルステライト被膜層を形成することなく、その後ＣＶＤ、ＰＶＤ、ゾルゲル法、鋼板酸化などの方法により別の下地被膜層を形成し、その上に、絶縁張力被膜層（絶縁張力被膜層Ａ）を形成してもよい。
　さらに、後述するように、ＣＶＤ、ＰＶＤ法を用いることで、Ａｌ、Ｃｒ、Ｔｉ、Ｖ、Ｍｎ、Ｎｂ、Ｈｆ、Ｔａ、Ｗやこれらの窒化物、酸化物、酸窒化物、炭窒化物を、膜厚方向に組成や濃度を変えながら製膜し、膜厚方向で異なる熱膨張係数をもったセラミックス層や、組成が連続的に変わるセラミックス層などの絶縁張力被膜層（絶縁張力被膜層Ａ）を形成することもできる。このように形成された絶縁張力被膜層Ａは、地鉄との密着性に優れるため、上記のような下地被膜層を形成することなく、直接、地鉄表面に絶縁張力被膜層Ａを形成することができる。
　本発明による絶縁張力被膜層Ａは、上述したように、絶縁張力被膜層Ａ中の膜厚方向で付与張力に傾斜を有するものである。本発明の絶縁被膜付き電磁鋼板は、前記絶縁張力被膜層Ａを含む絶縁被膜を電磁鋼板の表面に備える。前記絶縁被膜は、前記絶縁張力被膜層Ａだけで構成されてもよいし、前記絶縁張力被膜層Ａと鋼板との間にフォルステライト被膜層等の下地被膜が設けられてもよい。また、本発明の絶縁被膜付き電磁鋼板は、そのまま製品とされてもよいし、さらにその上にワニス等を塗布して形成した被膜を設けて製品とされてもよい。なお、上記の下地被膜や、ワニス等を塗布して形成した被膜は、本発明の絶縁張力被膜層Ａのように膜厚方向で付与張力に傾斜を有するものではない。
　上記のとおり、本発明の絶縁被膜付き電磁鋼板は、少なくとも電磁鋼板の片面に絶縁張力被膜層Ａを含む絶縁被膜が形成されてなる。そして、絶縁張力被膜層Ａの目付量をＭ、絶縁張力被膜層Ａが鋼板に対して与える張力をσＡとしたとき、絶縁張力被膜層Ａのうち表面から目付量Ｍ／２の絶縁被膜層が鋼板に与える張力が０．８０×σＡ以上であることを特徴とする。
　本発明では、絶縁張力被膜層Ａが鋼板に対して付与する張力は、圧延方向の張力とし、絶縁被膜付き電磁鋼板から作成した試験片（圧延方向２８０ｍｍ×圧延直角方向３０ｍｍ）の一方の面を粘着テープでマスキングしてから、もう一方の面の絶縁張力被膜層Ａをアルカリ、酸などを用いて除去し、次いで前記試験片の片端３０ｍｍを固定して試験片２５０ｍｍの部分を測定長さとしてそり量を測定し、下記式（Ｉ）を用いて算出するものとする。
鋼板への付与張力［ＭＰａ］＝鋼板ヤング率［ＧＰａ］×板厚［ｍｍ］×そり量［ｍｍ］÷（測定長さ［ｍｍ］）２×１０３・・・式（Ｉ）
ただし、鋼板ヤング率は、１３２ＧＰａとする。
　この際、試験片の片面から種々の除去率で絶縁張力被膜層Ａを除去し、そのときの付与張力を測定することで、絶縁張力被膜層Ａが鋼板に対して与える張力の絶縁張力被膜層Ａ中での分布を求めることができる。前記除去率は、例えば、試験片の片面から絶縁張力被膜層Ａを剥離する際に、試験片の片面の剥離液への浸漬条件（例えば１１０℃、２５質量％のＮａＯＨ水溶液に浸漬する時間）を調整することで任意に調節できる。
　そして、試験片の片面の絶縁張力被膜層Ａの目付量をＭとしたとき、例えば、Ｍ／３の目付量となる絶縁張力被膜層を試験片の片面から剥離して測定した際の付与張力が、絶縁張力被膜層Ａのうち表面から目付量Ｍ／３の絶縁張力被膜層が鋼板に与えていた張力に相当し、Ｍ／２の目付量となる絶縁張力被膜層を剥離して測定した際の付与張力が、絶縁張力被膜層Ａのうち表面から目付量Ｍ／２の絶縁被膜層が鋼板に与えていた張力に相当する。なお、Ｍの目付量、すなわち、試験片の片面から絶縁張力被膜層Ａを完全に剥離して測定した際の付与張力が、絶縁張力被膜層Ａ全体が鋼板に与えていた張力σＡに相当する。
　また、目付量Ｍ（ｇ／ｍ２）は、絶縁張力被膜層Ａの剥離前後の質量差（ｇ）と鋼板の片面表面積（ｍ２）から算出できる。
　本発明では、絶縁張力被膜層Ａの目付量をＭ、前記絶縁張力被膜層Ａが鋼板に対して与える張力をσＡとしたとき、絶縁張力被膜層Ａのうち表面から目付量Ｍ／２の絶縁張力被膜層が鋼板に与える張力（σＡ／２）がσＡの０．８０倍以上である必要がある。σＡ／２が０．８０倍未満の場合は、絶縁張力被膜層Ａの鋼板側半分が鋼板へ付与する張力（σＡ－σＡ／２）が依然高いために被膜界面（絶縁張力被膜層Ａとフォルステライト被膜層等の下地被膜との界面、もしくは絶縁張力被膜層Ａと地鉄との界面）でのせん断応力が大きくなってしまい、曲げ加工時に被膜が剥離しやすくなり密着性が劣ってしまう。より好ましくは、σＡ／２はσＡの０．８５倍以上である。また、上限についてはσＡ／２はσＡの１．００倍まで特に問題が生じることがないが、金属の熱膨張係数と非金属である絶縁被膜の熱膨張係数の差を考慮すると実現可能な上限値としては、σＡ／２はσＡの０．９８倍程度と考えられる。
　また、できるだけ絶縁張力被膜層Ａの表層側でより多くの鋼板付与張力を付与することが好ましい。そのため、絶縁張力被膜層Ａのうち表面から目付量Ｍ／３の絶縁張力被膜層が鋼板に与える張力（σＡ／３）は、σＡの０．５０倍以上であることが好ましく、０．６０倍以上であることがより好ましい。
　絶縁張力被膜層Ａを構成する材料としては、電気絶縁性が担保され、張力が付与される物質であれば、窒化物、硫化物、酸化物、無機物、有機物のいずれでも問題ない。ＣＶＤ、ＰＶＤ法をもちいると、Ａｌ、Ｃｒ、Ｔｉ、Ｖ、Ｍｎ、Ｎｂ、Ｈｆ、Ｔａ、Ｗやこれらの窒化物、酸化物、酸窒化物、炭窒化物などを比較的容易に製膜することができる。
　歪取焼鈍、常圧、大気中での使用等を考慮すると、絶縁張力被膜層Ａは、酸化物、好ましくは無機酸化物を主体とすることが好ましく、特にガラスまたはガラスセラミックスを主体とすることが好ましい。なお、本発明において主体とするとは、絶縁張力被膜層Ａ中に含まれる割合が、絶縁張力被膜層Ａの総質量に対して５０質量％以上であることを意味する。
　酸化物としては、リン酸塩、ホウ酸塩、ケイ酸塩等があげられるが、現在一般的に絶縁張力被膜として利用されている珪リン酸塩ガラスを用いることが好ましい。珪リン酸塩ガラスは大気中で吸湿する性質があるため、これを防止する目的でＭｇ、Ａｌ、Ｃａ、Ｂａ、Ｓｒ、Ｚｎ、Ｔｉ、Ｎｄ、Ｍｏ、Ｃｒ、Ｂ、Ｔａ、ＣｕおよびＭｎのうちから選ばれる１種以上の元素を含有させることが好ましい。また、前記元素に加え、任意の元素を含有させてもよい。例えば、表面の平滑度を向上させるため、Ｌｉ、Ｋのうちから選ばれる１種以上の元素を含有させることが好ましい。
　本発明のように絶縁張力被膜層Ａ内で鋼板への付与張力に傾斜をつける方法としては、例えば、絶縁張力被膜層Ａを、付与張力の異なる複数の珪リン酸塩ガラス層で形成する方法が挙げられる。この場合、絶縁張力被膜層Ａはガラスを主体して形成される。
　絶縁張力被膜層Ａ内で鋼板への付与張力に傾斜をつけるもっとも簡便な方法は、ガラス質の張力被膜内に異なる熱膨張係数をもったセラミックスの相を析出させ（つまりガラスセラミックスを主体とし）、その際のセラミックス相の分布を制御するものである。制御の方法としては絶縁張力被膜層Ａの鋼板側に熱膨張係数が大きいセラミックス相を析出させる方法もしくは絶縁張力被膜層Ａの表層側に低熱膨張のセラミックス相を析出させる方法が考えられるが、絶縁張力被膜層Ａ全体が鋼板に与える張力を考慮すると表層側に低熱膨張のセラミックス相を析出させる方法が好ましい。
　ガラスの結晶化はガラス内から生じる場合と、ガラス表面から生じる場合がある。本発明の場合、ガラス表面から結晶化を生じさせこれをガラス内方（つまり鋼板側）へ成長させるようにする方法をとるのが最も好ましい。
　また、絶縁張力被膜層Ａとして、上記のようなガラスセラミックスを形成する方法としては、例えば、リン酸、ホウ酸およびケイ酸のＭｇ、Ａｌ、Ｃａ、Ｂａ、Ｓｒ、Ｚｎ、Ｔｉ、Ｎｄ、Ｍｏ、Ｃｒ、Ｔａ、Ｃｕ、Ｍｎの塩のうちから選ばれる少なくとも１種と、コロイド状シリカと、を含む被膜形成用処理液を、電磁鋼板の少なくとも一方の表面に塗布し、前記塗布後、後述の方法で焼付する方法が挙げられる。なお、前記被膜形成用処理液には、さらに、リン酸、ホウ酸およびケイ酸の任意の塩、例えば、リン酸、ホウ酸およびケイ酸のＬｉ、Ｋ塩のうちから選ばれる１種以上を添加することができる。また、前記被膜形成用処理液には、さらに、任意の化合物、例えば、Ｌｉ、Ｋ、Ｍｇのうちから選ばれる１種以上を含む化合物を添加することができる。前記任意の化合物としては無機化合物が好ましい。
　上記のようなガラスセラミックスを形成する別の方法としては、リン酸のＭｇ、Ａｌ、Ｃａ、Ｂａ、Ｓｒ、Ｚｎ、Ｃｒ、Ｍｎの塩のうちから選ばれる少なくとも１種と、コロイド状シリカと、Ｔｉ、Ｎｄ、Ｍｏ、Ｂ、Ｔａ、Ｃｕのうちから選ばれる１種もしくは２種以上を含む化合物と、を含む被膜形成用処理液を、電磁鋼板の少なくとも一方の表面に塗布し、前記塗布後、後述の方法で焼付し、珪リン酸塩ガラスセラミックスを主体とする絶縁張力被膜層を形成する方法が挙げられる。なお、前記化合物としては無機化合物が好ましい。また、前記被膜形成用処理液には、さらに、任意の化合物、例えば、Ｌｉ、Ｋ、Ｍｇのうちから選ばれる１種以上を含む化合物を添加することができる。前記任意の化合物としては無機化合物が好ましい。
　絶縁張力被膜層Ａの焼付温度は焼付時に結晶化を生じさせる場合は、８００℃以上であることが好ましく、より高温である方が好ましい。しかしながら、温度が高くなりすぎると鋼板自身が焼き付け時にクリープ変形を起こしてしまうため、焼付温度は１１００℃以下であることが好ましく、１０５０℃以下であることがより好ましい。また、８００℃以上で結晶化が生じるためには、結晶核生成温度が６００℃～７００℃程度となるようコート液（被膜形成用処理液）の組成を調整する必要がある。一方で結晶核が過剰に生成した場合はガラス内で結晶化が生じる割合が高くなりすぎるため、本発明のように絶縁張力被膜層内で鋼板への付与張力に傾斜をつけることが難しくなる。これを避けるためには６００℃以上７００℃以下の温度域を１００℃／秒以上の加熱速度とすることが好ましい。より好ましくは１５０℃／秒以上である。６００℃以上７００℃以下の温度域での加熱速度の上限は特に限定されないが、実用上４００℃／秒以下が好ましく、より好ましくは３００℃／秒以下である。
　また、表面からの結晶化をさらに促進する方法として水を利用する方法があげられる。ガラス中に水が浸入するとガラスネットワークを切断するためガラスの粘度が低下する。これにより原子の移動が容易となり結晶化速度が促進する。８００℃以上の焼付で水によるガラス表面からの結晶化促進をおこなうためには、７００℃以上の温度域での雰囲気を、水蒸気露点：－２０℃以上の雰囲気とすることが好ましい。好ましくは水蒸気露点：－１５℃以上の雰囲気である。一方、水蒸気露点を高くし過ぎると鋼板表面に錆を生じるリスクが高くなるため、７００℃以上の温度域での雰囲気は、水蒸気露点：１０℃以下の雰囲気が好ましく、さらに好ましくは水蒸気露点：０℃以下の雰囲気である。
　さらに、鋼板への付与張力に傾斜を有する絶縁張力被膜層Ａを形成する他の方法としては、例えば、ＰＶＤ法やＣＶＤ法で、Ａｌ、Ｃｒ、Ｔｉ、Ｖ、Ｍｎ、Ｎｂ、Ｈｆ、Ｔａ、Ｗやこれらの窒化物、酸化物、酸窒化物、炭窒化物を、膜厚方向に組成や濃度を変えながら製膜し、異なる熱膨張係数をもったセラミックスを層構造とする方法やセラミックス層の中で組成を連続的に変更する方法などもあげられる。このように形成されたセラミックス層（絶縁張力被膜層Ａ）は、地鉄との密着性に優れるため、下地被膜層を形成することなく、直接、地鉄表面に絶縁張力被膜層Ａを形成することができる。
　絶縁張力被膜層Ａが鋼板に与える張力は１０ＭＰａ以上が好ましく、１２ＭＰａ以上がより好ましい。前記張力を高くすることで鉄損を低減したり、変圧器とした際の騒音を一層低減することができるからである。
　絶縁張力被膜層Ａの目付量は片面で２．０ｇ／ｍ２以上が好ましい。また、絶縁張力被膜層Ａの目付量は片面で１２．０ｇ／ｍ２以下が好ましい。目付量が２．０ｇ／ｍ２未満であると層間絶縁性がやや低下する。一方、目付量が１２．０ｇ／ｍ２超であると占積率が低下する。なお、占積率とはＪＩＳ　Ｃ　２５５０で定義される値である。より好ましくは絶縁張力被膜層Ａの目付量は片面で３．０ｇ／ｍ２以上である。また、より好ましくは絶縁張力被膜層Ａの目付量は片面で８．０ｇ／ｍ２以下である。
（実施例1）
　質量％で、Ｓｉ：３．２５％、Ｃ：０．０４％、Ｍｎ：０．０８％、Ｓ：０．００２％、ｓｏｌ．Ａｌ：０．０１５％、Ｎ：０．００６％、Ｃｕ：０．０５％、Ｓｂ：０．０１％を含有する珪素鋼板スラブを１１５０℃、２０分加熱後、熱間圧延して２．４ｍｍの板厚の熱延板とし、１０００℃、１分間の焼鈍を施した後、冷間圧延により０．２７ｍｍの最終板厚とし、得られた冷間圧延コイルの中央部から、１００ｍｍ×４００ｍｍサイズの試料を採取し、室温から８２０℃まで加熱速度８０℃／ｓにて昇温し、湿潤雰囲気下で８２０℃、６０秒の一次再結晶焼鈍をおこなった。引き続きＭｇＯ：１００質量部に対してＴｉＯ２を５質量部混合した焼鈍分離剤を水スラリ状にしてから塗布、乾燥した。この鋼板を３００℃から８００℃間を１００時間かけて昇温させた後、１２００℃まで５０℃／ｈｒで昇温させ、１２００℃で５時間焼鈍する最終仕上げ焼鈍を行いフォルステライトを主体とする下地被膜をもつ鋼板を準備した。
　続いて表２に記載の被膜形成用処理液を準備し、表３に記載の焼付条件にて絶縁張力被膜（絶縁張力被膜層Ａ）を被成した。すなわち、本実施例は、フォルステライト下地被膜層の上に、絶縁張力被膜層Ａを形成したものである。被膜形成用処理液の比重は、純水を用いて１．２０に調整した。前記処理液はロールコーターを用いて塗布し、各絶縁張力被膜層Ａの目付量は片面で４．５０ｇ／ｍ２とした。焼付雰囲気はＮ２：１００％雰囲気とし、７００℃以上の温度域での雰囲気露点（水蒸気露点）は表３に記載のとおりとした。
　かくして得られた各試料について、絶縁張力被膜層Ａが鋼板に対して与える張力の絶縁張力被膜層Ａ中での分布を上述した方法で測定した。なお、絶縁張力被膜層Ａの剥離量は、１１０℃、２５質量％のＮａＯＨ水溶液（剥離液）に浸漬する時間を調整することで調節した。また、絶縁被膜の密着性は、丸棒巻き付け法によって評価した。具体的には、試験片（圧延方向２８０ｍｍ×圧延直角方向３０ｍｍ）を、直径が５ｍｍの丸棒に巻き付け、１８０°曲げ戻した際に、目視にて被膜剥離の発生の有無を調査し、以下、丸棒の直径を５ｍｍ間隔であげていきながら同様の評価を行い、目視にて被膜剥離が生じない最小径（曲げ剥離径）にて評価した。この評価では、前記曲げ剥離径が小さいほど被膜密着性に優れると判断できる。結果を表３に併記する。
　表３に記載のとおり、σＡ／２がσＡの０．８０倍以上（σＡ／２／σＡが０．８０以上）である本発明では、曲げ剥離径が１５ｍｍ以下と優れた被膜密着性を有する。さらにσＡ／２がσＡの０．８５倍以上であれば曲げ剥離径が５ｍｍ以下とさらにいっそう良好な被膜密着性を有することがわかる。焼付条件の影響では６００℃以上７００℃以下の温度域の加熱速度が１００℃／ｓ以上で、かつ、焼付温度が８００℃以上の条件を満たせばσＡ／２／σＡが０．８０以上の絶縁被膜を得ることができることがわかる。
Figure JPOXMLDOC01-appb-T000002
  
Figure JPOXMLDOC01-appb-T000003
  
（実施例２）
　質量％で、Ｓｉ：３．２５％、Ｃ：０．０４％、Ｍｎ：０．０８％、Ｓ：０．００２％、ｓｏｌ．Ａｌ：０．０１５％、Ｎ：０．００６％、Ｃｕ：０．０５％、Ｓｂ：０．０１％を含有する珪素鋼板スラブを１１５０℃、２０分加熱後、熱間圧延して２．２ｍｍの板厚の熱延板とし、１０００℃、１分間の焼鈍を施した後、冷間圧延により０．２３ｍｍの最終板厚とし、引き続いて室温から８２０℃まで加熱速度５０℃／ｓにて昇温し、湿潤雰囲気下で８２０℃、６０秒の一次再結晶焼鈍をおこなった。その後ＭｇＯ：５０質量部に対してＡｌ２Ｏ３を１５０質量部、Ｎａ２Ｂ４Ｏ７・１０Ｈ２Ｏを１質量部混合した焼鈍分離剤を水スラリ状にしてから塗布、乾燥した。この鋼板を３００℃から８００℃間を１００時間かけて昇温させた後、１２００℃まで５０℃／ｈｒで昇温させ、１２００℃で５時間焼鈍する最終仕上げ焼鈍を行いコーディエライト（２ＭｇＯ・２Ａｌ２Ｏ３・５ＳｉＯ２）を主体とする結晶質の被膜をもつ鋼板を準備した。
　前記鋼板（圧延方向４００ｍｍ×圧延直角方向１００ｍｍ）から硫酸とフッ酸の混酸でコーディエライト被膜を剥離し、ＰＶＤ法にて鋼板表面に地鉄側を１００％ＴｉＮ、表面側を１００％ＡｌＮとし、かつ、その中間をＡｌＴｉＮの連続固溶体とする絶縁張力被膜（絶縁張力被膜層Ａ）を形成した。すなわち、本実施例は、地鉄表面に、直接、絶縁張力被膜層Ａを形成したものである。この際、Ｔｉターゲット、Ａｌターゲットのバイアス電圧をＯＮ／ＯＦＦするタイミングを変更して種々の濃度傾斜（Ａｌ／Ｔｉ比）をもつ絶縁被膜を有する試料を作製した。具体的には、表４中のＮｏ．３１を例にとると、Ｔｉターゲットのバイアス電圧をＯＮにしたタイミングを０秒とし、Ｔｉターゲットには０秒から４００秒まで電圧をかけ、Ａｌターゲットには、Ｔｉターゲットのバイアス電圧をＯＮにしたタイミングから３００秒後に電圧をかけ、３００秒から６００秒まで電圧をかけて絶縁張力被膜層Ａを形成することで、絶縁張力被膜層Ａ中に濃度傾斜（Ａｌ／Ｔｉ比）をもつ絶縁被膜を形成した。
　かくして得られた各試料について、絶縁張力被膜層Ａが鋼板に対して与える張力の絶縁張力被膜層Ａ中での分布を上述した方法で測定した。なお、絶縁張力被膜層Ａの剥離量は、３５質量％の過酸化水素（剥離液）に浸漬する時間を調整することで調節した。また、絶縁被膜の密着性を実施例１と同様にして評価した。結果を表４に併記する。
　表４に記載のとおり、σＡ／２／σＡが０．８０以上であれば、曲げ剥離径が１０ｍｍ以下と優れた被膜密着性を有する。さらにσＡ／２／σＡが０．８５以上であれば曲げ剥離径が５ｍｍ以下とさらにいっそう良好な被膜密着性を有することがわかる。
Figure JPOXMLDOC01-appb-T000004

Claims (6)

  1. 　絶縁張力被膜層Ａを含む絶縁被膜を少なくとも片面に有する絶縁被膜付き電磁鋼板であって、
    前記絶縁張力被膜層Ａの目付量をＭ、前記絶縁張力被膜層Ａが鋼板に対して与える張力をσＡとしたとき、
    前記絶縁張力被膜層Ａのうち表面から目付量Ｍ／２の絶縁張力被膜層が鋼板に与える張力が０．８０×σＡ以上である絶縁被膜付き電磁鋼板。
  2. 　前記絶縁張力被膜層Ａが、ガラスまたはガラスセラミックスを主体とする請求項１に記載の絶縁被膜付き電磁鋼板。
  3. 　前記絶縁張力被膜層Ａが、Ｍｇ、Ａｌ、Ｃａ、Ｂａ、Ｓｒ、Ｚｎ、Ｔｉ、Ｎｄ、Ｍｏ、Ｃｒ、Ｂ、Ｔａ、ＣｕおよびＭｎのうちから選ばれる１種以上の元素を含む珪リン酸塩ガラスまたは珪リン酸塩ガラスセラミックスである請求項１または２に記載の絶縁被膜付き電磁鋼板。
  4. 　絶縁張力被膜層Ａを含む絶縁被膜を少なくとも片面に有する絶縁被膜付き電磁鋼板の製造方法であって、
    前記絶縁張力被膜層Ａの目付量をＭ、前記絶縁張力被膜層Ａが鋼板に対して与える張力をσＡとしたとき、
    前記絶縁張力被膜層Ａのうち表面から目付量Ｍ／２の絶縁張力被膜層が鋼板に与える張力が０．８０×σＡ以上であり、
    前記絶縁張力被膜層Ａを、リン酸、ホウ酸およびケイ酸のＭｇ、Ａｌ、Ｃａ、Ｂａ、Ｓｒ、Ｚｎ、Ｔｉ、Ｎｄ、Ｍｏ、Ｃｒ、Ｔａ、Ｃｕ、Ｍｎの塩のうちから選ばれる少なくとも１種と、コロイド状シリカと、を含む被膜形成用処理液を、電磁鋼板の少なくとも一方の表面に塗布し、前記塗布後、６００℃以上７００℃以下の温度域を１００℃／秒以上の加熱速度で加熱したのち、８００℃以上で焼付けて形成する、絶縁被膜付き電磁鋼板の製造方法。
  5. 　絶縁張力被膜層Ａを含む絶縁被膜を少なくとも片面に有する絶縁被膜付き電磁鋼板の製造方法であって、
    前記絶縁張力被膜層Ａの目付量をＭ、前記絶縁張力被膜層Ａが鋼板に対して与える張力をσＡとしたとき、
    前記絶縁張力被膜層Ａのうち表面から目付量Ｍ／２の絶縁張力被膜層が鋼板に与える張力が０．８０×σＡ以上であり、
    前記絶縁張力被膜層Ａを、リン酸のＭｇ、Ａｌ、Ｃａ、Ｂａ、Ｓｒ、Ｚｎ、Ｃｒ、Ｍｎの塩のうちから選ばれる少なくとも１種と、コロイド状シリカと、Ｔｉ、Ｎｄ、Ｍｏ、Ｂ、Ｔａ、Ｃｕのうちから選ばれる１種もしくは２種以上を含む化合物と、を含む被膜形成用処理液を、電磁鋼板の少なくとも一方の表面に塗布し、前記塗布後、６００℃以上７００℃以下の温度域を１００℃／秒以上の加熱速度で加熱したのち、８００℃以上で焼付けて形成する、絶縁被膜付き電磁鋼板の製造方法。
  6. 　７００℃以上の温度域での雰囲気を、水蒸気露点：－２０℃以上１０℃以下の雰囲気とする請求項４または５に記載の絶縁被膜付き電磁鋼板の製造方法。
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JP2003301272A (ja) * 2002-04-11 2003-10-24 Nippon Steel Corp 低鉄損方向性電磁鋼板の製造方法
JP2007217758A (ja) 2006-02-17 2007-08-30 Nippon Steel Corp 方向性電磁鋼板とその絶縁被膜処理方法
JP2017061732A (ja) * 2015-09-25 2017-03-30 Ｊｆｅスチール株式会社 方向性電磁鋼板およびその製造方法
WO2017057513A1 (ja) * 2015-09-29 2017-04-06 新日鐵住金株式会社 方向性電磁鋼板、及び方向性電磁鋼板の製造方法

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CN115135794A (zh) * 2019-12-19 2022-09-30 Posco公司 无取向电工钢板及其制造方法
CN115135794B (zh) * 2019-12-19 2023-12-19 Posco公司 无取向电工钢板及其制造方法
WO2023195517A1 (ja) * 2022-04-06 2023-10-12 日本製鉄株式会社 方向性電磁鋼板及び絶縁被膜の形成方法
WO2023195518A1 (ja) * 2022-04-06 2023-10-12 日本製鉄株式会社 方向性電磁鋼板及び絶縁被膜の形成方法

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