Grain-oriented electrical steel sheet and insulating coating formation method

Abstract

This grain-oriented electrical steel sheet comprises: a base material steel sheet; a glass coating film that is formed on the surface of the base material steel sheet; and an insulating coating film that is formed on the surface of the glass coating film. The base material steel sheet has a thickness of 0.15 mm to 0.35 mm. The insulating coating film contains a metal phosphate, amorphous silica, and one or more oxo acid compounds selected from among those of tungsten, vanadium, molybdenum and zirconium. Relative to 100 parts by mass of the metal phosphate, the amount of the amorphous silica is 30 parts by mass to 150 parts by mass and the total amount of the oxo acid compounds is 1.0 part by mass to 50 parts by mass. The moisture content of the insulating coating film is 0% by mass to 0.04% by mass.

Description

[Technical Field]

[0001] The present invention relates to a grain-oriented electrical steel sheet and a method for forming an insulating coating on the grain-oriented electrical steel sheet. This application claims priority based on Japanese Patent Application No. 2023-061319, filed on April 5, 2023, the contents of which are incorporated herein by reference. [Background technology]

[0002] Grain-oriented electrical steel sheets are steel sheets that are primarily used as iron cores for transformers, etc. Such grain-oriented electrical steel sheets typically have a forsterite layer (also called a forsterite coating, glass coating, or primary coating) formed during high-temperature finish annealing, and an insulating coating that is formed by applying a treatment solution containing phosphates as its main component and then baking it during heat flattening of the steel sheet.

[0003] Insulating coatings are required to provide grain-oriented electrical steel sheets with electrical insulation and to reduce eddy current loss and improve core loss. In addition to insulation, insulating coatings are also required to have various other properties, such as corrosion resistance, heat resistance, slipperiness, and adhesion. This is necessary to facilitate various manufacturing processes when processing grain-oriented electrical steel sheets into iron cores for transformers and other devices. For example, if the insulating coating's heat resistance, slipperiness, and adhesion are poor, it may peel off during stress relief annealing in the manufacturing of the iron core, preventing the coating from demonstrating its inherent insulating properties or hindering smooth lamination of steel sheets, resulting in poor workability.

[0004] Furthermore, an important characteristic of the insulating coating of grain-oriented electrical steel sheets is the ability to apply tension to the steel sheets. Applying tension to steel sheets can improve the iron loss of grain-oriented electrical steel sheets by facilitating domain wall motion. Applying tension can also reduce magnetostriction, which is one of the main causes of noise emitted by transformers manufactured using grain-oriented electrical steel sheets in their iron cores.

[0005] To improve the various properties of grain-oriented electrical steel sheets as described above, specific techniques such as those disclosed in Patent Documents 1 to 7 below have been researched and developed.

[0006] For example, Patent Document 1 discloses that an insulating coating treatment solution containing a specific composition of phosphate, chromate, and colloidal silica as its main components is applied to a forsterite coating formed on the surface of a steel sheet after finish annealing, and then baked. The technology disclosed in Patent Document 1 allows an insulating coating with high tensile strength to be formed on the surface of the steel sheet, thereby reducing the iron loss and magnetostriction of the grain-oriented electrical steel sheet.

[0007] Patent Document 2 discloses a method in which a treatment solution containing ultrafine colloidal silica particles with a particle size of 8 μm or less, primary phosphate, and chromate in specific proportions is applied to a steel sheet and then baked. The technology disclosed in Patent Document 2 makes it possible to maintain the high tensile strength of the insulating coating and further improve the lubricity of the coating.

[0008] Furthermore, Patent Document 3 discloses a technology for forming a high-tensile insulating coating on the surface of a grain-oriented electrical steel sheet by applying a specific amount of insulating coating whose main components are phosphate, chromate, and colloidal silica with a glass transition point of 950°C to 1200°C.

[0009] The techniques disclosed in Patent Documents 1 to 3 above made it possible to form insulating coatings with significantly superior coating properties and improved coating tension. However, all of the techniques disclosed in Patent Documents 1 to 3 contain chromate, a chromium compound, in the insulating coating. In recent years, with increasing attention being paid to environmental issues, there has been a social demand to prohibit or restrict the use of compounds such as lead, chromium, and cadmium.

[0010] Therefore, technologies that can form good insulating coatings without containing the above-mentioned chromium compounds have been investigated.For example, Patent Document 4 discloses a method for treating an insulating coating on a grain-oriented electrical steel sheet, which involves baking at 300°C or higher a treatment solution containing 20 parts by mass of colloidal silica (SiO2 content), 10 to 120 parts by mass of aluminum phosphate, 2 to 10 parts by mass of boric acid, and 4 to 40 parts by mass in total of sulfates of one or more metal elements selected from Mg, Al, Fe, Co, Ni, and Zn.

[0011] Furthermore, Patent Document 5 discloses a technology relating to a coating agent for forming a film, which contains a mixture of boric acid and alumina sol and an organic solvent that is compatible with water, and has the effect of imparting tension to grain-oriented electrical steel sheets.

[0012] Patent Document 6 discloses a technique of adding an organic acid salt of one or more metal elements selected from Ca, Mn, Fe, Zn, Co, Ni, Cu, B, and Al to a surface treatment agent for grain-oriented electrical steel sheet containing phosphate and colloidal silica. Patent Document 6 also lists formates, acetates, oxalates, tartrates, lactates, citrates, succinates, and salicylates as examples of organic acid salts.

[0013] Furthermore, Patent Document 7 discloses a technology in which, in an insulating coating treatment agent for grain-oriented electrical steel sheets containing a phosphate and colloidal silica, the metal components in the phosphate are a combination of divalent metal elements, trivalent metal elements, and tetravalent or higher metal elements in specific proportions.

[0014] However, the insulating coating disclosed in Patent Document 4 sometimes reduces the corrosion resistance of the steel sheet due to sulfate ions in the sulfate salt. Furthermore, the technology disclosed in Patent Document 5 has poor corrosion resistance and a baking temperature that is too high, making the steel sheet susceptible to scratches. Furthermore, the technology disclosed in Patent Document 6 has poor solution stability, with the organic acid in the organic salt discoloring the surface treatment agent solution. Furthermore, the technology disclosed in Patent Document 7 has difficulty in uniform application because the preparation of the coating solution is complicated and the concentration of the coating solution cannot be increased.

[0015] In addition, the chromate-free insulating coatings disclosed in Patent Documents 4 to 7 were unable to impart sufficient tension to the steel sheet, and therefore could not be said to have sufficiently improved the iron loss of the grain-oriented electrical steel sheet. Therefore, further improvement was needed in the technology related to the insulating coatings of these grain-oriented electrical steel sheets. [Prior art documents] [Patent documents]

[0016] [Patent Document 1] Japan Special Publication No. 53-28375 [Patent Document 2] Japanese Patent Publication No. 61-41778 [Patent Document 3] Japanese Patent Application Publication No. 11-071683 [Patent Document 4] Japan Special Publication No. 57-9631 [Patent Document 5] Japanese Patent Application Publication No. 7-278828 [Patent Document 6] Japanese Patent Publication No. 2000-178760 [Patent Document 7] Japanese Patent Application Publication No. 2010-13692 Summary of the Invention [Problem to be solved by the invention]

[0017] As noted above, there is room for improvement in chromate-free insulating coatings. Furthermore, when attempting to improve the above-mentioned characteristics of an insulating coating that does not contain chromate, one possible method is to incorporate a phosphate containing a specific metal element. However, this method has the problem of reducing the chemical stability of the coating and increasing the amount of phosphoric acid eluted from the insulating coating.

[0018] Therefore, the present invention aims to provide a grain-oriented electrical steel sheet having a chromate-free insulating coating that has corrosion resistance, coating adhesion, and coating tension that are equal to or better than conventional ones, in which the amount of phosphoric acid eluted from the insulating coating is small (excellent elution resistance), and to provide a method for forming such an insulating coating (insulating coating forming method). [Means for solving the problem]

[0019] The present inventors have investigated the suppression of phosphoric acid elution from insulating coatings that do not contain chromate, and have found that the elution of phosphoric acid is suppressed from insulating coatings obtained by applying an insulating coating solution that contains an oxo acid compound of a specific metal element.

[0020] The present invention has been made in light of the above findings. [1] A grain-oriented electrical steel sheet according to one embodiment of the present invention comprises a base steel sheet, a glass coating formed on the surface of the base steel sheet, and an insulating coating formed on the surface of the glass coating, wherein the base steel sheet has a thickness of 0.15 to 0.35 mm, the insulating coating contains a metal phosphate, amorphous silica, and one or more oxo acid compounds of tungsten, vanadium, molybdenum, and zirconium, and the amorphous silica is present in an amount of 30 to 150 parts by mass and the oxo acid compounds are present in a total amount of 1.0 to 50 parts by mass per 100 parts by mass of the metal phosphate, and the insulating coating has a moisture content of 0 to 0.04% by mass. [2] In the grain-oriented electrical steel sheet according to [1], the oxo acid compound may be a tungstate, a phosphotungstate, a silicotungstate, a vanadate, a phosphomolybdate, or a zirconate. [3] Another aspect of the present invention provides a method for forming an insulating coating, comprising: a solution preparation step of preparing an insulating coating solution having a solids concentration of 8 to 50 mass%. The solution contains 30 to 150 mass parts of colloidal silica (in terms of silica content) and 1.0 to 50 mass parts in total of an oxo acid compound of one or more of tungsten, vanadium, molybdenum, and zirconium per 100 mass parts of a metal phosphate; and a coating and drying step of applying the insulating coating solution to a steel sheet, heating the solution to a temperature range of 800 to 900°C at a heating rate of 40 to 200°C / sec between 100 and 600°C, and maintaining the solution at that temperature range for 5 to 90 seconds. [4] In the insulating coating forming method described in [3], in the solution preparing step, 1 to 5 parts by mass of phosphonic acid may be added to the insulating coating solution per 100 parts by mass of the metal phosphate. [Effects of the Invention]

[0021] According to the above-described aspects of the present invention, it is possible to provide a grain-oriented electrical steel sheet in which the amount of phosphoric acid eluted from the insulating coating is small, and a method for forming the insulating coating. DETAILED DESCRIPTION OF THE INVENTION

[0022] A grain-oriented electrical steel sheet according to one embodiment of the present invention (grain-oriented electrical steel sheet according to the present embodiment) comprises a base steel sheet, a glass coating formed on the surface of the base steel sheet, and an insulating coating formed on the surface of the glass coating. In addition, in the grain-oriented electrical steel sheet according to this embodiment, the thickness of the base steel sheet is 0.15 to 0.35 mm, the insulating coating contains a metal phosphate, amorphous silica, and one or more oxoacid compounds of tungsten, vanadium, molybdenum, and zirconium, and the moisture content of the insulating coating is 0 to 0.04 mass%. Each of these will be explained below.

[0023] [Base material steel plate] The grain-oriented electrical steel sheet according to this embodiment is characterized by its insulating coating, and the base steel sheet of the grain-oriented electrical steel sheet is not limited in chemical composition and may be within a known range. For example, to obtain the properties generally required of grain-oriented electrical steel sheets, the following chemical components may be included. In this embodiment, % indicating the content of each element is % by mass unless otherwise specified.

[0024] C: 0.010% or less Carbon (C) is an element effective for controlling the structure of steel sheets in the manufacturing process up to the completion of the decarburization annealing step. However, if the C content exceeds 0.010%, the magnetic properties of the finished grain-oriented electrical steel sheet will deteriorate. Therefore, in the base steel sheet of the grain-oriented electrical steel sheet according to this embodiment, the C content is preferably 0.010% or less. The C content is more preferably 0.005% or less. The lower the C content, the better; however, even if the C content is reduced to less than 0.0001%, the effect of structural control will saturate and the manufacturing cost will simply increase. Therefore, the C content may be 0.0001% or more.

[0025] Si: 2.00 to 6.00% Silicon (Si) is an element that increases the electrical resistance of grain-oriented electrical steel sheets and improves their core loss characteristics. If the Si content is less than 2.00%, a sufficient eddy current loss reduction effect cannot be obtained. Therefore, the Si content is preferably 2.00% or more. The Si content is more preferably 2.50% or more, and even more preferably 3.00% or more. On the other hand, if the Si content exceeds 6.00%, the grain-oriented electrical steel sheet becomes embrittled and the threading property deteriorates significantly. Furthermore, the workability of the grain-oriented electrical steel sheet deteriorates, and the steel sheet may break during rolling. Therefore, the Si content is preferably 6.00% or less. The Si content is more preferably 5.00% or less, and even more preferably 4.00% or less.

[0026] Mn: 0.01 to 0.50% Mn (manganese) is an element that combines with S to form MnS during the manufacturing process. These precipitates function as inhibitors (suppressors of normal grain growth) and cause secondary recrystallization in steel. Mn also improves the hot workability of steel. If the Mn content is less than 0.01%, the above-mentioned effects cannot be fully achieved. Therefore, the Mn content is preferably 0.01% or more. The Mn content is more preferably 0.02% or more. On the other hand, if the Mn content exceeds 0.50%, secondary recrystallization does not occur, and the magnetic properties of the steel deteriorate. Therefore, in the base steel sheet of the grain-oriented electrical steel sheet according to this embodiment, the Mn content is preferably 0.50% or less. The Mn content is more preferably 0.20% or less, and even more preferably 0.10% or less.

[0027] N: 0.010% or less N (nitrogen) is an element that bonds with Al during the manufacturing process to form AlN, which functions as an inhibitor. However, if the N content exceeds 0.010%, the magnetic properties will be reduced due to the inhibitor remaining in excess in the base steel sheet. Therefore, in the base steel sheet of the grain-oriented electrical steel sheet according to this embodiment, the N content is preferably 0.010% or less. The N content is more preferably 0.008% or less. On the other hand, the lower limit of the N content is not particularly specified, but reducing it to less than 0.001% would only increase the manufacturing cost, so the N content may be 0.001% or more.

[0028] sol.Al: 0.020% or less Al (aluminum) is an element that bonds with N to form AlN, which functions as an inhibitor, during the manufacturing process of grain-oriented electrical steel sheets. However, if the sol.Al (acid-soluble aluminum) content of the base steel sheet exceeds 0.020%, the magnetic properties will be reduced due to the excess inhibitor remaining in the base steel sheet. Therefore, in the base steel sheet of the grain-oriented electrical steel sheet according to this embodiment, the sol.Al content is preferably 0.020% or less. The sol.Al content is more preferably 0.010% or less, and even more preferably less than 0.001%. There is no particular lower limit for the sol.Al content, but reducing it to less than 0.0001% will only increase manufacturing costs. Therefore, the sol.Al content may be 0.0001% or more.

[0029] S: 0.010% or less S (sulfur) is an element that combines with Mn during the manufacturing process to form MnS, which functions as an inhibitor. However, if the S content exceeds 0.010%, the magnetic properties will be reduced due to the excess remaining inhibitor. Therefore, in the base steel sheet of the grain-oriented electrical steel sheet according to this embodiment, the S content is preferably 0.010% or less. The S content in the grain-oriented electrical steel sheet is preferably as low as possible, for example, less than 0.001%. However, reducing the S content in the grain-oriented electrical steel sheet to less than 0.0001% will only increase the manufacturing cost. Therefore, the S content in the grain-oriented electrical steel sheet may be 0.0001% or more.

[0030] P:0.030% or less P (phosphorus) is an element that reduces workability in rolling. By setting the P content to 0.030% or less, excessive reduction in rolling workability can be prevented, and fractures during manufacturing can be suppressed. From this perspective, the P content is preferably set to 0.030% or less. The P content is more preferably set to 0.020% or less, and further preferably set to 0.010% or less. The lower limit of the P content may include 0%, but since the detection limit of chemical analysis is 0.0001%, the substantial lower limit of the P content in practical steel sheets is 0.0001%. P is also an element that has the effect of improving texture and magnetic properties. To achieve this effect, the P content may be set to 0.001% or more, or even 0.005% or more.

[0031] Remainder: Fe and impurities The chemical composition of the base steel sheet of the grain-oriented electrical steel sheet according to this embodiment may contain the above-mentioned elements, with the remainder being Fe and impurities. However, for the purpose of improving magnetic properties, etc., Cu, Cr, Sn, Se, Sb, and Mo may also be contained in the ranges shown below. These elements may also be contained as impurities. Since they do not necessarily need to be contained, the lower limit is 0%. Furthermore, even if other elements than these are contained, for example, one or more of W, Nb, Ti, Ni, Bi, Co, and V in a total amount of 1.0% or less (regardless of whether they are intentionally added as impurities), this does not impair the effects of the grain-oriented electrical steel sheet according to this embodiment. Here, impurities refer to elements that are mixed in from raw materials such as ore or scrap, or the manufacturing environment, when the base steel sheet is industrially manufactured, and are permissible to be contained in amounts that do not adversely affect the function of the grain-oriented electrical steel sheet according to this embodiment.

[0032] Cr: 0 to 0.50% Cr (chromium) is an element that contributes to increasing the Goss orientation occupancy rate in the secondary recrystallized structure and improves magnetic properties. To achieve this effect, the Cr content is preferably 0.01% or more, more preferably 0.02% or more, and even more preferably 0.03% or more. On the other hand, if the Cr content exceeds 0.50%, Cr oxides are formed, resulting in a deterioration in magnetic properties. Therefore, the Cr content is preferably 0.50% or less. The Cr content is more preferably 0.30% or less, and even more preferably 0.10% or less.

[0033] Sn: 0 to 0.50% Sn (tin) is an element that contributes to improving magnetic properties by controlling the primary recrystallization structure. To obtain the effect of improving magnetic properties, the Sn content is preferably 0.01% or more. The Sn content is more preferably 0.02% or more, and even more preferably 0.03% or more. On the other hand, if the Sn content exceeds 0.50%, secondary recrystallization becomes unstable and magnetic properties deteriorate. Therefore, the Sn content is preferably 0.50% or less. The Sn content is more preferably 0.30% or less, and even more preferably 0.10% or less.

[0034] Cu: 0 to 0.50% Cu (copper) is an element that contributes to increasing the Goss orientation occupancy rate in the secondary recrystallized structure. Cu is an optional element in the base steel sheet according to this embodiment. Therefore, the lower limit of its content is 0%, but in order to obtain the above-mentioned effects, the Cu content is preferably 0.01% or more. The Cu content is more preferably 0.02% or more, and even more preferably 0.03% or more. On the other hand, if the Cu content exceeds 0.50%, the steel sheet becomes embrittled during hot rolling. Therefore, in the base steel sheet of the grain-oriented electrical steel sheet according to this embodiment, the Cu content is preferably 0.50% or less. The Cu content is more preferably 0.30% or less, and even more preferably 0.10% or less.

[0035] Se: 0 to 0.020% Se (selenium) is an element that has the effect of improving magnetic properties. Therefore, it may be contained. When Se is contained, the content is preferably 0.001% or more in order to effectively exhibit the effect of improving magnetic properties. The Se content is preferably 0.003% or more, and more preferably 0.006% or more. On the other hand, if the Se content exceeds 0.020%, the adhesion of the glass coating deteriorates. Therefore, the Se content is preferably 0.020% or less. The Se content is more preferably 0.015% or less, and even more preferably 0.010% or less.

[0036] Sb: 0 to 0.500% Sb (antimony) is an element that has the effect of improving magnetic properties. Therefore, it may be contained. When Sb is contained, the content is preferably 0.005% or more in order to effectively exhibit the effect of improving magnetic properties. The Sb content is more preferably 0.010% or more, and even more preferably 0.020% or more. On the other hand, if the Sb content exceeds 0.500%, the adhesion of the glass coating significantly deteriorates. Therefore, the Sb content is preferably 0.500% or less. The Sb content is more preferably 0.300% or less, and even more preferably 0.100% or less.

[0037] Mo: 0 to 0.10% Mo (molybdenum) is an element that has the effect of improving magnetic properties. Therefore, it may be contained. When Mo is contained, the Mo content is preferably 0.01% or more in order to effectively exhibit the effect of improving magnetic properties. The Mo content is more preferably 0.02% or more, and even more preferably 0.03% or more. On the other hand, if the Mo content exceeds 0.10%, the cold rolling property deteriorates and there is a possibility of fracture. Therefore, the Mo content is preferably 0.10% or less. The Mo content is more preferably 0.08% or less, and further preferably 0.05% or less.

[0038] As described above, the chemical composition of the base steel sheet of the grain-oriented electrical steel sheet in this embodiment may, for example, contain the above-mentioned essential elements with the balance consisting of Fe and impurities, or may contain the above-mentioned essential elements and further contain one or more optional elements with the balance consisting of Fe and impurities.

[0039] The chemical composition of the base steel sheet of the grain-oriented electrical steel sheet according to this embodiment can be measured after removing the glass coating and insulating coating formed on the surface. Specifically, the insulating coating is removed by immersing the grain-oriented electrical steel sheet in an aqueous sodium hydroxide solution containing 10 to 20 mass % of NaOH at 80 to 90°C for 7 to 10 minutes. The grain-oriented electrical steel sheet from which the insulating coating has been removed is washed with water, and then dried with a hot air blower for just under 1 minute (for example, 5 to 60 seconds).The dried grain-oriented electrical steel sheet (grain-oriented electrical steel sheet without the insulating coating) is immersed in an aqueous hydrochloric acid solution containing 5 to 10 mass% HCl at 70 to 90°C for 1 to 10 minutes to remove the glass coating. After immersion, the base steel sheet is rinsed with water, and then dried with a hot air blower for just under 1 minute (for example, 5 to 60 seconds). Through the above steps, the base steel sheet can be taken out from the grain-oriented electrical steel sheet. The chemical composition of such a base steel plate is determined by a known elemental analysis method. Specifically, chips are generated from the base steel plate using a drill, the chips are collected, and the collected chips are dissolved in acid to obtain a solution. The solution is subjected to ICP-AES to perform elemental analysis of the chemical composition. Here, the Si content in the chemical composition of the base steel plate is determined by the method (silicon determination method) specified in JIS G1212 (1997). Specifically, when the above-mentioned chips are dissolved in acid, silicon oxide is precipitated, and this precipitate (silicon oxide) is filtered out with filter paper and its mass is measured to determine the Si content. The carbon and sulfur contents are determined by the well-known high-frequency combustion method (combustion-infrared absorption method). Specifically, the above solution is combusted in an oxygen stream by high-frequency heating, and the generated carbon dioxide and sulfur dioxide are detected to determine the carbon and sulfur contents. The N content is determined using the well-known inert gas fusion-thermal conductivity method.

[0040] <Thickness> The thickness of the base steel sheet is 0.15 to 0.35 mm, taking into consideration its application to transformer cores. The thinner the sheet thickness, the greater the effect of reducing eddy current loss and the better the iron loss, so the preferred upper limit of the thickness of the base steel sheet is 0.35 mm. However, special equipment is required to manufacture base steel sheet with a thickness of less than 0.15 mm, which is undesirable from a production standpoint, as it increases manufacturing costs. Therefore, the industrially preferred lower limit of the thickness is 0.15 mm.

[0041] [Glass coating] The grain-oriented electrical steel sheet according to this embodiment has a glass coating (sometimes called a forsterite coating) formed on the surface of a base steel sheet. The glass coating may be a known coating. Generally, it is an inorganic coating whose main component is magnesium silicate (forsterite). The glass coating is formed during finish annealing by a reaction between the annealing separator containing magnesia (MgO) applied to the surface of the base steel sheet and the components of the surface of the base steel sheet, and has a composition derived from the components of the annealing separator and the base steel sheet, and is composed of a structure including the Mg2SiO4 phase (50% or more by area) as the main phase and the MgAl2O4 phase. In addition to these phases, precipitates may be present at a rate of 1% or less. The glass coating contributes to improving the adhesion of the insulating coating.

[0042] [Insulating coating] In the grain-oriented electrical steel sheet according to this embodiment, the insulating coating is formed on the surface of the glass coating. The insulating coating contains a metal phosphate, amorphous silica, and one or more oxoacid compounds of tungsten, vanadium, molybdenum, and zirconium, and the proportions of the metal phosphate, amorphous silica, and oxoacid compounds are 30 to 150 parts by mass of amorphous silica and 1.0 to 50 parts by mass of oxoacid compounds in total per 100 parts by mass of the metal phosphate. The metal phosphate is not limited to, but may be, for example, aluminum phosphate or magnesium phosphate. However, from the viewpoint of moisture resistance, the proportion of magnesium in the metal phosphate is preferably 50% by mass or less, and more preferably 30% by mass or less (for example, 70% by mass or more of aluminum phosphate and 30% by mass or less of magnesium phosphate). If the proportion of amorphous silica derived from colloidal silica in the insulating coating solution is too high, cracks in the coating may occur and the moisture content of the insulating coating may increase. On the other hand, if the proportion of amorphous silica is too low, the proportion of phosphate may become higher than necessary, increasing the moisture content of the insulating coating.

[0043] As a result of investigations by the present inventors, it is assumed that the reason why the amount of phosphoric acid elution increases when chromic acid is not contained is that when an insulating coating solution that does not contain chromic acid is applied to a steel sheet having a glass coating, the forsterite layer on the surface of the steel sheet reacts with the solution to produce magnesium phosphate, which is highly hygroscopic and soluble. Therefore, in the grain-oriented electrical steel sheet according to this embodiment, a substance with higher acidity is blended into the insulating coating to suppress reaction with forsterite, thereby achieving both high coating tension and suppression of phosphoric acid elution. A specific transition metal oxoacid compound is used as a substance with higher acidity that does not degrade the properties of the coating. Specifically, the oxoacid compound contains a total of 1.0 to 50 parts by mass of one or more oxoacid compounds of tungsten, vanadium, molybdenum, and zirconium per 100 parts by mass of the metal phosphate. In this embodiment, the transition metal oxoacid compound is a transition metal element to which an oxygen atom is directly bonded. If the proportion of the oxo acid compound of one or more of tungsten, vanadium, molybdenum, and zirconium is too low, the moisture content of the insulating coating increases, and the elution resistance of the insulating coating decreases, whereas if the proportion is too high, the corrosion resistance decreases and the solution becomes unstable. The oxoacid compound must be one or more oxoacids of tungsten, vanadium, molybdenum, and zirconium. Other oxoacids do not provide sufficient resistance to phosphoric acid elution. The oxo acid compound is preferably a tungsten or vanadium oxo acid compound. For example, the oxo acid compound is a tungstate, a phosphotungstate, a silicotungstate, a vanadate, a phosphomolybdate, or a zirconate. In terms of solution stability, a phosphotungstate or a tungstate is preferred. A vanadium oxo acid compound is more preferred. In addition, in terms of miscibility with phosphates, sodium salts such as sodium vanadate and sodium tungstate are preferred. If tungsten, vanadium, molybdenum and / or zirconium are contained in a state other than an oxo acid compound, the desired effect cannot be obtained.

[0044] The oxoacid compound is present together with the metal phosphate as a matrix (i.e., in a molecular form, not in a particulate form). For example, if the oxoacid compound is present in a particulate form, the desired effect cannot be obtained. Furthermore, if the oxo acid compound is an ammonium compound, the corrosion resistance may decrease and the moisture content of the insulating coating may decrease, so it is preferable that the oxo acid compound is not an ammonium compound.

[0045] When a highly hygroscopic compound such as boric acid is contained together with an oxo acid compound, the moisture content of the coating film tends to increase. Therefore, it is preferable that no other compounds are contained, or if any, that the amount of such other compounds is 5 parts by mass or less per 100 parts by mass of the metal phosphate.

[0046] The proportions of the metal phosphate, amorphous silica, and oxoacid compound in the insulating coating can be determined by the following method. Using an energy dispersive X-ray analyzer, it is possible to detect and analyze each element in the insulating coating, thereby calculating the proportion of phosphate, silica, and oxoacid compounds. Furthermore, using X-ray crystal structure analysis, it is possible to calculate the proportion of amorphous silica in the silica. When detecting each element using an energy dispersive X-ray analyzer, it is preferable to analyze about three locations at a magnification of 1000x and calculate the average value. Furthermore, when performing crystal structure analysis, it is preferable to use, for example, a SmartLab manufactured by RIGAKU Corporation, with a Cu tube, a voltage of 40 kV, a current of 30 mA, a measurement angle (2θ) of 5 to 90°, a step of 0.02°, a scan speed of 1° / min, an entrance slit of 1 / 2°, and a receiving slit of 20 mm.

[0047] <Moisture content> The insulating coating of the grain-oriented electrical steel sheet according to this embodiment has a moisture content of 0 to 0.04 mass %. The elution of phosphoric acid can be suppressed by reducing the moisture content of the insulating coating, and a significant effect can be achieved by keeping the moisture content at 0.04 mass % or less. Although the moisture content of a typical insulating coating is about 0.05 to 0.15% by mass, by adjusting the content of the oxo acid compound and the baking conditions to a predetermined range according to the content of the oxo acid compound, the moisture content can be reduced to 0.04% by mass or less, preferably 0.03% by mass or less, and more preferably 0.02% by mass or less.

[0048] The water content can be determined by the Karl Fischer method. Specifically, approximately 3 g of a sample taken from a grain-oriented electrical steel sheet with an insulating coating is placed in a sealed heating furnace and heated to 105°C in a nitrogen gas stream to vaporize the water. The vaporized water is passed through 150 ml of indicator solution containing Karl Fischer reagent for 30 minutes to dissolve the water in the reagent solution. Quantitative analysis is then performed using the Karl Fischer titration method described in JIS K0113 (2005).

[0049] <Amount of insulating coating> In the grain-oriented electrical steel sheet according to this embodiment, the coating weight of the insulating coating is not particularly limited. For example, the coating weight of the insulating coating may be 1 to 10 g / m 2 That's fine.

[0050] [Manufacturing method] The grain-oriented electrical steel sheet according to this embodiment can achieve the above-described effects regardless of the manufacturing method, but can be preferably manufactured by a manufacturing method including the following steps, for example. (i) a hot rolling process in which the billet is heated and hot-rolled into a hot-rolled sheet; (ii) a hot-rolled sheet annealing step of annealing the hot-rolled sheet; (iii) a pickling step of pickling the hot-rolled sheet after the hot-rolled sheet annealing step; (iv) a cold rolling step in which the hot-rolled sheet after the pickling step is cold-rolled once or twice or more times with annealing interposed therebetween to obtain a cold-rolled sheet; (v) a decarburization annealing step of subjecting the cold-rolled sheet to decarburization annealing; (vi) a finish annealing step in which an annealing separator is applied to the front and back surfaces of the cold-rolled sheet after the decarburization annealing step, which is the base steel sheet, and then finish annealing is performed; (vii) a solution preparation step of preparing an insulating coating solution; (viii) a coating and drying step of applying the insulating coating solution to the steel sheet after the final annealing step and heating it to form an insulating coating. (ix) a magnetic domain refining step of irradiating the surface of the insulating coating with an energy beam. However, the conditions for the steps other than (vii) the solution preparation step and (viii) the application and drying step (collectively referred to as the insulating coating formation step) related to the formation of the insulating coating are not limited, and the steps can be carried out under known manufacturing conditions for grain-oriented electrical steel sheets.

[0051] [Hot rolling process] In the hot rolling process, a steel billet such as a slab having a predetermined chemical composition (a chemical composition corresponding to the chemical composition of the base steel sheet of the grain-oriented electrical steel sheet according to this embodiment) is heated and hot-rolled to form a hot-rolled sheet. The heating temperature is, for example, 1000 to 1400°C.

[0052] The chemical composition of the steel slab to be subjected to hot rolling may be determined in accordance with the chemical composition desired to be obtained as a grain-oriented electrical steel sheet, taking into consideration changes in the chemical composition in each process.

[0053] The method for obtaining a steel slab is not limited. For example, molten steel having a predetermined chemical composition may be produced and used to produce the slab. Slabs may be produced by continuous casting, or ingots may be produced using the molten steel and then bloomed to produce the slab. Alternatively, slabs may be produced by other methods. The thickness of the steel billet is not particularly limited, but is, for example, 150 to 350 mm. The thickness of the steel billet is preferably 220 to 280 mm. As the steel billet, so-called thin slabs having a thickness of 10 to 70 mm may be used. Hot rolling produces what is called a hot-rolled sheet (hot-rolled steel sheet). The thickness (finishing thickness) of the hot-rolled sheet is not particularly limited. However, the hot-rolled sheet is annealed, pickled, and then cold-rolled. It is known that the so-called cold-rolling reduction ratio affects the magnetic properties of grain-oriented electrical steel sheets, and the thickness of the hot-rolled sheet is selected taking into account the required cold-rolling reduction ratio relative to the final thickness. For example, the finishing thickness of the hot-rolled sheet is 2.0 to 4.0 mm.

[0054] [Hot-rolled sheet annealing process] In the hot-rolled sheet annealing process, the steel sheet (hot-rolled sheet) after the hot rolling process is annealed. By performing such annealing treatment, recrystallization occurs in the steel sheet structure, making it possible to achieve good magnetic properties. In the hot-rolled sheet annealing step of this embodiment, the hot-rolled sheet manufactured through the hot rolling step may be annealed according to a known method. The means for heating the hot-rolled sheet during annealing is not particularly limited, and known heating methods can be adopted. For example, so-called continuous annealing may be used, or the hot-rolled sheet may be coiled and subjected to batch annealing. The annealing conditions are also not particularly limited, but for example, the hot-rolled sheet may be annealed in a temperature range of 900 to 1200°C for 10 seconds to 5 minutes. The atmosphere is not particularly limited, but it is preferable to suppress oxidation of the steel sheet, and therefore, the annealing is preferably performed in a non-oxidizing atmosphere such as nitrogen, argon, or hydrogen.

[0055] [Pickling process] In the pickling process, scale (oxides) formed on the surface of the steel sheet during the hot rolling and hot-rolled sheet annealing is removed. A known method is used in the pickling process of this embodiment. Known acids such as hydrochloric acid, sulfuric acid, and nitric acid are used as the pickling solution. Known pickling inhibitors, pickling accelerators, and the like may be added to the pickling solution as needed. Furthermore, before contacting the steel sheet with the pickling solution, physical treatments such as shot blasting of the steel sheet may be performed before pickling in order to penetrate the pickling solution into the interface between the scale and the steel sheet and improve the pickling efficiency.

[0056] [Cold rolling process] In the cold rolling process, the steel sheet after the pickling process is cold rolled to obtain a cold-rolled sheet. The cold rolling may be a single cold rolling (a series of cold rolling without intermediate annealing) or may be multiple cold rollings with intermediate annealing between them, with the cold rolling being interrupted and at least one or two or more intermediate annealings being performed before the final pass of the cold rolling process. The cold rolling conditions may be in accordance with known methods. The cold rolling reduction of grain-oriented electrical steel sheet has a significant effect on its magnetic properties. The final rolling reduction has a particularly large effect, and the final rolling reduction can be set to 80 to 95%. The final rolling reduction is the cumulative rolling reduction of cold rolling, and in the case where intermediate annealing is performed, it is the cumulative rolling reduction of cold rolling after final intermediate annealing. When intermediate annealing is performed, for example, the steel sheet is held at a temperature of 800 to 1200°C for 5 to 180 seconds. The annealing atmosphere is not particularly limited, but it is preferable to perform the annealing in a non-oxidizing atmosphere such as nitrogen, argon, or hydrogen to prevent oxidation of the steel sheet. The annealing method may be so-called continuous annealing, batch annealing in a coil shape, or other methods. The number of times intermediate annealing is performed is preferably three or less, taking production costs into consideration.

[0057] [Decarburization annealing process] In the decarburization annealing process, the cold-rolled sheet after the grinding process is subjected to decarburization annealing. This decarburization annealing removes carbon (C), which has a negative effect on magnetic properties, from the steel sheet, and also causes primary recrystallization of the cold-rolled sheet. The decarburization annealing conditions are not limited, but annealing is performed in a nitrogen-hydrogen mixed atmosphere for decarburization, with the oxygen potential increased by humidification. In addition, since it is necessary to form a primary recrystallized structure, the humidification temperature (dew point) is determined from the viewpoint of the annealing temperature required for recrystallization and the oxygen potential that allows decarburization at that annealing temperature. The annealing temperature is, for example, about 700 to 900° C., and since annealing is generally performed in a continuous annealing process, soaking is performed for about 60 seconds.

[0058] [Finishing annealing process] In the final annealing step, an annealing separator is applied to the cold-rolled sheet after the decarburization annealing step, and the cold-rolled sheet is then final annealed. Because final annealing requires a long annealing time, the steel sheet is usually wound into a coil and batch annealed. Because the temperature of the steel sheet rises to around 1200°C, an annealing separator is applied to prevent the coiled steel sheet from seizing. MgO is generally used as the annealing separator. By using an annealing separator whose main component is MgO, a glass coating is formed on the surface of the steel sheet after final annealing. Furthermore, in the final annealing process, the steel sheet is heated to cause secondary recrystallization of the primary recrystallized grains obtained in the decarburization annealing process, obtaining crystal grains with Goss orientation. Furthermore, by holding the steel sheet at an annealing temperature close to 1200°C for a specified time, precipitates in the steel, such as nitrides (e.g., AlN) and sulfides (e.g., MnS), which have completed their role as inhibitors, are removed (purified) so that they do not adversely affect the magnetic properties. The conditions for finish annealing are not limited, but the temperature is raised from room temperature at a rate of 10 to 100°C / h, and in the temperature range of 900 to 1000°C, where secondary recrystallization in the Goss orientation generally occurs, the temperature is raised at a rate of 5 to 20°C / h to promote preferential growth in the Goss orientation (secondary recrystallization), and then, as mentioned above, the inhibitor, which has completed its role, is purified at around 1200°C (for example, 1150 to 1250°C).Then, the coil is slowly cooled in a non-oxidizing atmosphere such as hydrogen or nitrogen, and then removed from the furnace.

[0059] <Solution preparation process> In the solution preparation step, an insulating coating solution having a solids concentration of 8 to 50 mass% is prepared, which contains 30 to 150 mass parts of colloidal silica in terms of silica content and 1.0 to 50 mass parts in total of oxo acid compounds of one or more of tungsten, vanadium, molybdenum, and zirconium in terms of solid content, per 100 mass parts of metal phosphate. The metal phosphate, colloidal silica, and oxo acid compound are blended in proportions to obtain an insulating coating containing the metal phosphate, amorphous silica, and oxo acid compound in the above-mentioned ratios. Here, the oxo acid compound is in a hydrated state in the solution, rather than in an emulsion, dispersion, or suspension state, to form the matrix of the insulating coating. If the solids concentration is less than 8% by mass, the aqueous solution applied to the steel sheet becomes unstable, causing coating defects such as patterns and uneven coating. On the other hand, if the solids concentration is more than 50% by mass, the pot life of the aqueous solution will be shortened. In addition, the solids concentration also affects the amount of oxo acid compound remaining in the insulating coating, so this point must also be taken into consideration when setting the concentration.

[0060] It is preferable to add 1 to 5 parts by mass of phosphonic acid to the insulating coating solution per 100 parts by mass of metal phosphate, which has the effect of improving the coatability. On the other hand, as mentioned above, it is preferable that the insulating coating solution does not contain boric acid or the like, which has high hygroscopicity.

[0061] <Coating and drying process> In the coating and drying process, the insulating coating solution is applied to the steel sheet (a steel sheet with a glass coating formed on the surface of the base steel sheet after finish annealing), and the sheet is heated to a temperature range of 800 to 900°C at a heating rate of 40 to 200°C / second between 100 and 600°C, and then held at this temperature range for 5 to 90 seconds to form the insulating coating (drying and baking). If the heating rate between 100 and 600°C is less than 40°C / sec, moisture will not evaporate easily from the coating surface, increasing elution and causing a high moisture content.On the other hand, if the heating rate exceeds 200°C / sec, bumping and other problems will occur easily, increasing the moisture content and causing a decrease in corrosion resistance. Furthermore, if the heating temperature is below 800°C, the polymerization of the phosphate and oxoacid will not proceed easily, resulting in a decrease in the coating tension.If the heating temperature exceeds 900°C, thermal strain will occur in the steel sheet, causing magnetostriction. Furthermore, if the holding time is less than 5 seconds, the polymerization of the phosphate and the oxoacid does not proceed easily, causing a decrease in the film tension, whereas if it exceeds 90 seconds, the film is prone to cracking, causing a decrease in corrosion resistance.

[0062] <Magnetic domain refining process> In the magnetic domain refining process, the surface of the insulating coating (the surface of the insulating coating of a grain-oriented electrical steel sheet comprising a base steel sheet, a glass coating, and an insulating coating) is irradiated with energy rays to perform 180° magnetic domain refinement. By refining the magnetic domains, it is possible to further reduce the iron loss of the grain-oriented electrical steel sheet. The magnetic domain refinement may be performed by any known method, such as forming linear or point-like grooves extending in a direction intersecting the rolling direction at predetermined intervals along the rolling direction to narrow the width of the 180° magnetic domains (refining the 180° magnetic domains), or forming linear or point-like stress-strain portions or grooves extending in a direction intersecting the rolling direction at predetermined intervals along the rolling direction to narrow the width of the 180° magnetic domains (refining the 180° magnetic domains). When forming stress-strained portions, laser beam irradiation, electron beam irradiation, etc. can be applied. When forming grooves, mechanical groove formation methods using gears, etc., chemical groove formation methods using electrolytic etching, and thermal groove formation methods using laser irradiation can be applied. If the insulating coating is damaged by the formation of stress-strained portions or grooves, and the insulating properties and other characteristics are deteriorated, the insulating coating may be formed again to repair the damage. [Example]

[0063] A slab was obtained by casting molten steel containing 3.2 mass% Si, 0.027 mass% sol. Al, 0.08 mass% Mn, 0.008 mass% N, 0.08 mass% C, with the balance being Fe and impurities. After heating the slab, it was hot rolled to obtain a steel plate (hot-rolled plate) with a thickness of 2.0 mm. This steel sheet was annealed at 1100°C for 5 minutes (hot-rolled sheet annealing). The hot-rolled and annealed steel sheets were subjected to pickling treatment and then cold-rolled to form steel sheets (cold-rolled sheets) with a thickness of 0.23 mm. This steel sheet was subjected to decarburization annealing by holding it at 850°C for 3 minutes. After decarburization annealing, an annealing separator containing MgO as the main component (containing 90% by mass or more) was applied, and the steel was then heated to 1200°C and subjected to finish annealing by holding at that temperature in a hydrogen stream for 20 hours. After finish annealing, a specimen measuring 7 cm in the width direction and 30 cm in the rolling direction was cut out from the steel sheet, and the annealing separator remaining on the surface was removed by water washing and light pickling, but the glass film formed during finish annealing was left in place. Thereafter, the specimens were annealed (stress relief annealing) by holding them at 850°C for 2 hours in a nitrogen stream to obtain test specimens.

[0064] The oxoacid compounds of the metal elements shown in Table 1 were added to an insulating coating treatment solution containing metal phosphate and colloidal silica as the main components in the proportions shown in Table 2. The insulating coating treatment solution was then applied to the specimens after stress relief annealing, and the specimens were dried to form an insulating coating on the surface. The amount of the insulating coating applied was 5 g / m. 2 (In Table 2, when "Type: Ratio of Metal Phosphate" is used, Al: 100% means that 100% of the metal phosphate is aluminum phosphate, and Al: 75%, Mg 25% means that 75% of the metal phosphate is aluminum phosphate and 25% is magnesium phosphate.) In this way, a grain-oriented electrical steel sheet was obtained that included a steel sheet (so-called base steel sheet), a glass coating, and an insulating coating. The grain-oriented electrical steel sheet thus obtained was subjected to a magnetic domain refinement treatment by irradiating it with a laser beam. The laser irradiation was performed using a continuous laser in a direction perpendicular to the rolling direction, with an irradiation pitch of 6 mm and an energy density of 2.0 mJ / mm. 2 The experiment was carried out under the following conditions.

[0065] [Table 1]

[0066] [Table 2]

[0067] The chemical composition of the base steel sheet of the obtained grain-oriented electrical steel sheet contained 3.2 mass% Si, 0.01 mass% sol.Al, 0.07 mass% Mn, less than 0.001 mass% N, 0.001 mass% C, and the remainder Fe and impurities.

[0068] The contents (parts by mass) of amorphous silica and one or more oxoacid compounds of tungsten, vanadium, molybdenum, and zirconium in the insulating coating were measured using an energy dispersive X-ray analyzer as described above, per 100 parts by mass of the metal phosphate. The oxoacid compounds were found to be compatible with the metal phosphate and formed the matrix of the insulating coating. The results are shown in Table 3.

[0069] After the insulating coating was formed, the grain-oriented electrical steel sheets were kept at room temperature for 24 hours, and the moisture content of the insulating coating was measured by the Karl Fischer method (amperometric titration method). Specifically, approximately 3 g of the sample was placed in a sealed heating furnace and heated to 105°C in a nitrogen gas stream to vaporize the water content. The vaporized water content was passed through 150 ml of an indicator solution containing Karl Fischer reagent for 30 minutes to dissolve the water in the reagent solution, after which quantitative analysis was performed using the Karl Fischer titration method described in JIS K0113 (2005). The results are shown in Table 3.

[0070] [Table 3]

[0071] The resulting grain-oriented electrical steel sheets were evaluated for coating tension, coating adhesion, magnetic properties, corrosion resistance, and elution resistance in the following manner. For the measurements, corrosion resistance was measured after the insulating coating was formed and kept at room temperature for 24 hours, but for the coating tension, coating adhesion, magnetic properties, and elution resistance, measurements were taken after leaving the samples at a constant temperature and humidity of 50°C and 80% for 168 hours in order to measure properties after moisture absorption.

[0072] <Coating tension> The coating tension was calculated by back-calculating from the state of curvature when one side of the insulating coating was peeled off. If the obtained film tension was 4.0 MPa or more, it was determined that the film had sufficient tension.

[0073] <Coating adhesion> Adhesion was evaluated by a bending adhesion test using a 10 mm diameter cylinder after stress relief annealing of a 30 mm wide, 300 mm long sample in a nitrogen stream at 800°C for 2 hours. The evaluation criteria were as follows depending on the peel width, and a rating of 3 or higher (3 to 5) was considered to be sufficient coating adhesion. 5: No peeling 4: Almost no peeling (peeled area is 1 mm or less) 3: Peeling is observed with a width of more than 1mm but less than 1 / 3 2: Peeling is observed over a width of 1 / 3 to 1 / 2 1: Peeling over 1 / 2 width to entire surface

[0074] <Magnetic properties> B8 (magnetic flux density at a magnetizing force of 800 A / m) and W17 / 50 (iron loss per mass at a magnetic flux density amplitude of 1.7 T and 50 Hz) were measured. These characteristic values ​​were measured using a single sheet magnetic property measurement method (Single Sheet Tester: SST) in accordance with JIS C2556 (2015).

[0075] <Corrosion resistance> After forming the insulating coating, the grain-oriented electrical steel sheets were kept at room temperature for 24 hours, and then a 5% NaCl aqueous solution was allowed to fall naturally onto the samples for 7 hours in a 35°C atmosphere in accordance with the salt spray test method described in JIS Z2371 (2015). The rust area was evaluated on a 10-point scale. The evaluation criteria were as follows: A rating of 5 or more (5 to 10) was considered to indicate sufficient corrosion resistance. 10: No rust occurred 9: Very little rust (area rate 0.10% or less) 8: Area ratio of rusted surface = over 0.10% and 0.25% or less 7: Area ratio of rusted area = over 0.25% and 0.50% or less 6: Area ratio of rusted surface = over 0.50% and 1.0% or less 5: Area ratio of rusted surface = over 1.0% and 2.5% or less 4: Area ratio of rusted surface = 2.5% to 5% 3: Area ratio of rusted surface = more than 5% but less than 10% 2: Area ratio of rusted surface = over 10% and less than 25% 1: Area ratio of rusted surface = over 25%

[0076] <Elution resistance> The amount of phosphoric acid eluted from the sample was measured. The sample was boiled in boiling pure water for 10 minutes, the amount of phosphorus dissolved in the pure water was measured, and the amount of phosphorus dissolved was obtained by dividing the amount of phosphorus by the area of ​​the insulating coating of the boiled grain-oriented electrical steel sheet. The amount of phosphorus dissolved in the pure water was measured by cooling the pure water (solution) into which the phosphorus had dissolved, and then diluting the cooled solution with pure water to measure the phosphoric acid concentration of the sample using ICP-AES. Elution amount: 40mg / m 2 If the resistance was less than this, it was determined that the resistance to elution was excellent.

[0077] [Table 4]

[0078] As can be seen from the results in Tables 1 to 4, inventive examples 1 to 8, metal phosphate, amorphous silica, and one or more oxoacid compounds of tungsten, vanadium, molybdenum, and zirconium were contained in specified proportions, and the moisture content of the insulating coating was 0.04 mass% or less. As a result, grain-oriented electrical steel sheets were obtained that had sufficient corrosion resistance, coating adhesion, and coating tension (equal to or better than conventional ones) and had insulating coatings with excellent elution resistance. Furthermore, these grain-oriented electrical steel sheets also had magnetic properties that were equal to or better than conventional ones. On the other hand, in Comparative Examples 1, 3, 5, 7, and 15, the proportion of the oxo acid compound in the insulating coating was too low and the water content exceeded 0.04 mass %, so the resistance to elution was poor. In Comparative Examples 2 and 4, the amount of oxo acid compound was excessive, and the corrosion resistance and film tension were poor. In Comparative Examples 6 and 8, the amount of oxo acid compound was excessive, and the film tension was poor. In Comparative Examples 9 to 12, the oxo acid compound was not an oxo acid compound of one or more of tungsten, vanadium, molybdenum, and zirconium, and the moisture content of the insulating coating was high, resulting in poor elution resistance. In Comparative Example 13, the insulating coating had an insufficient proportion of amorphous silica and a high water content, resulting in poor corrosion resistance and elution resistance. In Comparative Example 14, the proportion of amorphous silica in the insulating coating was too high, and the coating adhesion was poor. In Comparative Example 16, the heating rate during coating and drying was slow, and the moisture content of the insulating coating was high, resulting in poor resistance to elution. In Comparative Example 17, the heating rate during coating and drying was high, causing bumping and other problems, and the moisture content of the insulating coating was high. As a result, the coating adhesion and corrosion resistance were poor. [Industrial Applicability]

[0079] The present invention provides a grain-oriented electrical steel sheet with an insulating coating that leaches out a small amount of phosphoric acid, and a method for forming the insulating coating, and is therefore highly industrially applicable.

Claims

1. A base steel plate; a glass coating formed on the surface of the base steel sheet; an insulating coating formed on the surface of the glass coating; and The thickness of the base steel plate is 0.15 to 0.35 mm, the insulating coating comprises a metal phosphate, amorphous silica, and one or more oxoacid compounds of tungsten, vanadium, molybdenum, and zirconium, and the amorphous silica is present in an amount of 30 to 150 parts by mass and the oxoacid compounds in total are present in an amount of 1.0 to 50 parts by mass per 100 parts by mass of the metal phosphate; The moisture content of the insulating coating is 0 to 0.04% by mass. A directional electrical steel sheet characterized by:

2. the oxo acid compound is a tungstate, a phosphotungstate, a silicotungstate, a vanadate, a phosphomolybdate, or a zirconate; The grain-oriented electrical steel sheet according to claim 1 .

3. a solution preparation step of preparing an insulating coating solution containing 30 to 150 parts by mass of colloidal silica in terms of silica content and 1.0 to 50 parts by mass in total of an oxo acid compound of one or more of tungsten, vanadium, molybdenum, and zirconium per 100 parts by mass of metal phosphate, the solution having a solids concentration of 8 to 50% by mass; a coating and drying step of applying the insulating coating solution to a steel sheet, heating the steel sheet to a temperature range of 800 to 900°C at a heating rate of 40 to 200°C / sec between 100 and 600°C, and maintaining the steel sheet at the temperature range for 5 to 90 seconds; having A method for forming an insulating film.

4. In the solution preparation step, 1 to 5 parts by mass of phosphonic acid is added to the insulating coating solution relative to 100 parts by mass of the metal phosphate.

4. The method for forming an insulating coating according to claim 3.

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