Grain-oriented electrical steel sheet and method for forming insulating coating

Abstract

This grain-oriented electromagnetic steel sheet comprises a base steel sheet and an insulating film that is formed on the surface of the base steel sheet; the insulating film comprises an intermediate layer that is formed on the base steel sheet side, while containing a crystalline metal phosphate salt, and a tension coating layer that is formed on the surface side of the insulating film; the intermediate layer has an average thickness of 0.3 to 10.0 μm; the insulating film has an average thickness of 2.0 to 10.0 μm; the crystalline metal phosphate salt in the intermediate layer is composed of one or more substances selected from among zinc phosphate, manganese phosphate, iron phosphate and zinc calcium phosphate; the tension coating layer contains a metal phosphate salt and silica; and the content of the silica in the tension coating layer is from 20 to 60% 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. This application claims priority based on Japanese Patent Application No. 2021-064964, filed on April 6, 2021, the contents of which are incorporated herein by reference. [Background technology]

[0002] Grain-oriented electrical steel sheets are mainly used in transformers. Transformers are continuously excited for a long period of time from installation to disposal, and continue to generate energy loss. Therefore, the energy loss when magnetized with AC, that is, core loss, is the main index that determines the performance of a transformer.

[0003] In order to reduce the iron loss of grain-oriented electrical steel sheets, (a) {110} <001> To date, many technologies have been developed to (a) increase the concentration of elements in the orientation (Goss orientation), (b) increase the content of solid solution elements such as Si to increase the electrical resistance of the steel sheet, or (c) reduce the thickness of the electrical steel sheet.

[0004] Also, applying tension to steel sheets is effective in reducing iron loss. Forming a coating made of a material with a smaller thermal expansion coefficient than steel sheets on the surface of the steel sheets at high temperatures is an effective means of reducing iron loss. A forsterite-based coating (inorganic coating) with excellent coating adhesion is produced during the finish annealing process of electrical steel sheets by reaction between oxides on the steel sheet surface and an annealing separator, and is a coating that can apply tension to steel sheets.

[0005] For example, the method disclosed in Patent Document 1, in which a coating liquid mainly composed of colloidal silica and phosphate is baked onto the surface of a steel sheet to form an insulating coating, is an effective method for reducing iron loss because it is highly effective in applying tension to the steel sheet. Therefore, the general method for manufacturing grain-oriented electrical steel sheets is to leave the forsterite-based coating formed in the final annealing process and apply an insulating coating mainly composed of phosphate on top of it.

[0006] However, in recent years, there has been an increasing demand for smaller and higher-performance transformers, and grain-oriented electrical steel sheets are required to have excellent high-magnetic field iron loss, so that the iron loss is good even when the magnetic flux density is high, in order to make the transformers smaller. At the same time, it has been revealed in recent years that forsterite-based coatings hinder the movement of magnetic domain walls, adversely affecting iron loss. In grain-oriented electrical steel sheets, magnetic domains change as the magnetic domain walls move under an alternating magnetic field. Smooth and rapid movement of the magnetic domain walls is effective in reducing iron loss, but the forsterite-based coating is itself a non-magnetic material and has an uneven structure at the steel sheet / coating interface, which is thought to have an adverse effect on iron loss because it hinders the movement of the magnetic domain walls. Therefore, as a means for improving high magnetic field iron loss, research is being conducted on a method for removing the inorganic coating by mechanical means such as polishing, or by chemical means such as pickling, as well as a technology for manufacturing grain-oriented electrical steel sheets that do not have an inorganic coating by preventing the formation of an inorganic coating during high-temperature finish annealing, and a technology for making the steel sheet surface in a mirror-like state (in other words, a technology for magnetically smoothing the steel sheet surface).

[0007] As a technique for preventing the formation of an inorganic coating, for example, Patent Document 2 discloses a technique in which after normal finish annealing, the steel sheet is pickled to remove surface formations, and then chemically or electrolytically polished to make the steel sheet surface mirror-finished. It has been found that a more excellent iron loss improvement effect can be obtained by forming a tensioned insulating coating on the surface of a grain-oriented electrical steel sheet obtained by such a known method that does not have an inorganic coating. Furthermore, the tensioned insulating coating can impart various properties such as corrosion resistance, heat resistance, and slipperiness in addition to improving iron loss.

[0008] However, inorganic coatings not only have the effect of exhibiting insulating properties, but also have the effect of serving as an intermediate layer that ensures adhesion when forming a tension coating (tension-applying insulating coating). In other words, inorganic coatings are formed in a state in which they penetrate deeply into the steel sheet, and therefore have excellent adhesion to the steel sheet, which is a metal. Therefore, when a tension-applying coating (tension coating) containing colloidal silica, phosphate, or the like as a main component is formed on the surface of an inorganic coating, the coating has excellent adhesion. On the other hand, since it is generally difficult for metals and oxides to bond with each other, it has been difficult to ensure sufficient adhesion between the tensile coating and the steel sheet surface in the absence of an inorganic coating. For this reason, when forming a tensile coating on a grain-oriented electrical steel sheet that does not have an inorganic coating, the provision of a layer that substitutes for the role of the intermediate layer of the inorganic coating has been considered.

[0009] For example, Patent Document 3 discloses a technique in which a grain-oriented electrical steel sheet having no inorganic coating is annealed in a weak reducing atmosphere to selectively thermally oxidize silicon inevitably contained in the silicon steel sheet, thereby forming a SiO2 layer on the steel sheet surface, and then a tension-imparting insulating coating is formed. Patent Document 4 discloses a technique in which a grain-oriented electrical steel sheet having no inorganic coating is anodically treated in a silicate aqueous solution to form a SiO2 layer on the steel sheet surface, and then a tension-imparting insulating coating is formed.

[0010] Furthermore, Patent Document 5 discloses a technique for ensuring the adhesion of a tensioned insulating coating by applying a coating that serves as an intermediate layer in advance when forming the tensioned coating.

[0011] Patent Document 6 discloses a grain-oriented electrical steel sheet comprising a base steel sheet and a tension-applying insulating coating, in which the tension-applying insulating coating is present on the surface of the grain-oriented electrical steel sheet, and an iron-based oxide layer having a thickness of 100 to 500 nm is present between the base steel sheet and the tension-applying insulating coating. [Prior art documents] [Patent documents]

[0012] [Patent Document 1] Japanese Patent Publication No. 48-039338 [Patent Document 2] Japanese Patent Publication No. 49-96920 [Patent Document 3] Japanese Patent Application Publication No. 6-184762 [Patent Document 4] Japanese Patent Application Publication No. 11-209891 [Patent Document 5] Japanese Patent Publication No. 5-279747 [Patent Document 6] Japanese Patent Application Publication No. 2020-111814 Summary of the Invention [Problem to be solved by the invention]

[0013] However, the technique disclosed in Patent Document 3 requires preparation of annealing equipment capable of controlling the atmosphere in order to perform annealing in a weakly reducing atmosphere, which poses a problem in terms of processing costs. Also, in the technique disclosed in Patent Document 4, in order to obtain a SiO2 layer on the steel sheet surface that maintains sufficient adhesion to the tension-applied insulating coating by performing anodic electrolysis in a silicate aqueous solution, it is necessary to prepare a new electrolysis equipment, which poses a problem in terms of processing costs. Furthermore, the technique disclosed in Patent Document 5 has a problem in that it is not possible to maintain a tensioned insulating coating having a large tension with good adhesion. Furthermore, in the technology disclosed in Patent Document 6, in order to form an iron-based oxide layer, the grain-oriented electrical steel sheet after surface treatment is heat-treated at a steel sheet temperature of 700 to 900° C. for 5 to 60 seconds in an atmosphere with an oxygen concentration of 1 to 21 volume % and a dew point of −20 to 30° C. Therefore, when manufacturing steel sheet having an inorganic coating on the same line, it is necessary to change the atmosphere in the annealing furnace, which results in inferior workability.

[0014] As described above, assuming a method that does not impose equipment constraints or deteriorate workability, it has been difficult to provide a grain-oriented electrical steel sheet that does not have an inorganic coating, has excellent coating adhesion, has high coating tension, and has excellent magnetic properties. Therefore, an object of the present invention is to provide a grain-oriented electrical steel sheet that does not have an inorganic coating and that has excellent coating adhesion, excellent coating tension, and excellent magnetic properties. Another object of the present invention is to provide a method for forming an insulating coating for such grain-oriented electrical steel sheet. [Means for solving the problem]

[0015] The present inventors have conducted research into the above-mentioned problems, and as a result, have found that in a grain-oriented electrical steel sheet that does not have a forsterite-based coating, by providing an intermediate layer made of a crystalline metal phosphate between a base steel sheet and a tension coating, it is possible to improve the coating adhesion, coating tension, and magnetic properties.

[0016] The present invention has been made based on the above findings. The gist of the present invention is as follows. [1] A grain-oriented electrical steel sheet according to one embodiment of the present invention comprises a base steel sheet and an insulating coating formed on a surface of the base steel sheet, the insulating coating being formed on the base steel sheet side, an intermediate layer containing a crystalline metal phosphate, and a tensile coating layer formed on the surface side of the insulating coating, the intermediate layer having an average thickness of 0.3 to 10.0 μm, the insulating coating having an average thickness of 2.0 to 10.0 μm, the crystalline metal phosphate of the intermediate layer being one or more of zinc phosphate, manganese phosphate, iron phosphate, and zinc calcium phosphate, the crystalline metal phosphate is not a hydrate, The tensile coating layer contains a metal phosphate and silica, and the content of the silica in the tensile coating layer is 20 to 60 mass %. [2] A method for forming an insulating coating according to another aspect of the present invention is a method for forming the insulating coating provided on the grain-oriented electrical steel sheet according to the above item [1], comprising the steps of: applying an annealing separator containing 10 to 100 mass% of Al2O3 to a steel sheet, drying the steel sheet, and then performing a finish annealing process; removing excess annealing separator from the steel sheet after the finish annealing process; and subjecting the steel sheet after the annealing separator removal process to a bath at a liquid temperature of 40 to 85°C and containing 5 to 50 mass% of a metal phosphate. The method includes an immersion step of immersing the steel sheet in a treatment liquid for 5 to 150 seconds, a drying step of removing the steel sheet after the immersion step from the treatment liquid, removing excess treatment liquid, and drying the steel sheet, and a tensile coating layer formation step of applying a coating liquid containing a metal phosphate and colloidal silica such that the colloidal silica is 30 to 150 parts by mass per 100 parts by mass of the metal phosphate to the steel sheet after the drying step, drying the steel sheet, and then maintaining the steel sheet at a sheet temperature of 700 to 950°C for 10 to 120 seconds. [3] In the method for forming an insulating coating described in [2] above, the annealing separator may further contain one or both of MgO: 5 to 90 mass % and chloride: 0.5 to 10.0 mass %. Effect of the Invention

[0017] According to the above aspect of the present invention, it is possible to provide a grain-oriented electrical steel sheet that does not have a forsterite-based coating and that has excellent coating adhesion, excellent coating tension, and excellent magnetic properties. Also, according to the above aspect of the present invention, it is possible to provide a method for forming an insulating coating that is included in a grain-oriented electrical steel sheet that has excellent coating adhesion and excellent magnetic properties. [Brief description of the drawings]

[0018] [Figure 1] 1 is an example of a cross-sectional view of a grain-oriented electrical steel sheet according to an embodiment of the present invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0019] We will now describe a grain-oriented electrical steel sheet according to one embodiment of the present invention (grain-oriented electrical steel sheet according to this embodiment) and a method for manufacturing the grain-oriented electrical steel sheet according to this embodiment, including a method for forming the insulating coating provided on the grain-oriented electrical steel sheet according to this embodiment. First, the grain-oriented electrical steel sheet according to this embodiment will be described.

[0020] As shown in Figure 1, the grain-oriented electrical steel sheet 100 of this embodiment has a base steel sheet 1 and an insulating coating 2 formed on the surface of the base steel sheet 1, and does not have a forsterite-based coating on the surface of the base steel sheet 1. In addition, this insulating coating 2 has a tensile coating layer 22 formed on the surface side of the insulating coating 2 (i.e., the surface side of the directional electrical steel sheet 100), and an intermediate layer 21 formed on the base steel sheet 1 side and containing a crystalline metal phosphate.

[0021] <Base material steel plate> (chemical composition) The grain-oriented electrical steel sheet 100 according to this embodiment is significantly characterized by the structure of the insulating coating 2 formed on the surface of the base steel sheet 1, and the base steel sheet 1 included in the grain-oriented electrical steel sheet 100 is not limited in terms of its chemical composition, which may be within a known range. To obtain characteristics generally required of a grain-oriented electrical steel sheet, it is preferable for the chemical components to contain the following. In this embodiment, % relating to the chemical components is % by mass unless otherwise specified.

[0022] C: 0.010% or less C (carbon) is an element effective for controlling the structure of the steel sheet in the process up to the completion of the decarburization annealing process in the manufacturing process. However, if the C content exceeds 0.010%, the magnetic properties of the finished grain-oriented electrical steel sheet 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 more preferable it is, but even if the C content is reduced to less than 0.0001%, the effect of controlling the structure is saturated and the manufacturing cost is simply increased. Therefore, the C content may be 0.0001% or more.

[0023] Si: 2.50-4.00% 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 2.50%, a sufficient eddy current loss reduction effect cannot be obtained. Therefore, the Si content is preferably 2.50% or more. The Si content is more preferably 2.70% or more, and further preferably 3.00% or more. On the other hand, if the Si content exceeds 4.00%, the grain-oriented electrical steel sheet becomes embrittled and the sheet passing property is significantly deteriorated. In addition, the workability of the grain-oriented electrical steel sheet is deteriorated, and the steel sheet may break during rolling. For this reason, the Si content is preferably 4.00% or less. The Si content is more preferably 3.80% or less, and further preferably 3.70% or less.

[0024] Mn: 0.01 to 0.50% Mn (manganese) is an element that combines with S to form MnS during the manufacturing process. This precipitate functions as an inhibitor (a suppressor of normal grain growth) and causes secondary recrystallization in the steel. Mn is also an element that improves the hot workability of the steel. If the Mn content is less than 0.01%, the above-mentioned effects cannot be sufficiently obtained. 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 further preferably 0.10% or less.

[0025] N: 0.010% or less N (nitrogen) is an element that combines with Al in the manufacturing process to form AlN, which functions as an inhibitor. However, if the N content exceeds 0.010%, the inhibitor remains in the grain-oriented electrical steel sheet in excess, resulting in a deterioration in magnetic properties. 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, and therefore the N content may be set to 0.001% or more.

[0026] Sol.Al: 0.020% or less Sol.Al (acid-soluble aluminum) is an element that combines with N to form AlN, which functions as an inhibitor, during the manufacturing process of the grain-oriented electrical steel sheet. However, if the sol.Al content of the base steel sheet exceeds 0.020%, the inhibitor remains excessively in the base steel sheet, and the magnetic properties are deteriorated. 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 further preferably less than 0.001%. The lower limit of the sol.Al content is not particularly specified, but even if it is reduced to less than 0.0001%, the manufacturing cost will only increase. Therefore, the sol.Al content may be 0.0001% or more.

[0027] S: 0.010% or less S (sulfur) is an element that combines with Mn in the manufacturing process to form MnS, which functions as an inhibitor. However, if the S content exceeds 0.010%, the magnetic properties are reduced due to the 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. It is more preferable that the S content in the grain-oriented electrical steel sheet is as low as possible. For example, it is less than 0.001%. However, even if the S content in the grain-oriented electrical steel sheet is reduced to less than 0.0001%, the manufacturing cost will only increase. Therefore, the S content in the grain-oriented electrical steel sheet may be 0.0001% or more.

[0028] 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 (basic elements), with the balance being Fe and impurities. However, in order to improve magnetic properties, etc., one or more of Sn, Cu, Se, and Sb may be further contained in the ranges shown below. Furthermore, even if other elements such as W, Nb, Ti, Ni, Co, V, Cr, and Mo are contained in a total of 1.0% or less (regardless of whether they are intentionally added or contained as impurities), this does not impair the effect 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, 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.

[0029] Sn: 0 to 0.50% Sn (tin) is an element that contributes to improving magnetic properties through controlling the primary recrystallization structure. In order 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 further preferably 0.03% or more. On the other hand, if the Sn content exceeds 0.50%, the secondary recrystallization becomes unstable and the magnetic properties deteriorate. Therefore, the Sn content is preferably 0.50% or less. The Sn content is more preferably 0.30% or less, and further preferably 0.10% or less.

[0030] Cu: 0-0.50% Cu (copper) is an element that contributes to an increase in the Goss orientation occupancy rate in the secondary recrystallized structure. In order to obtain the above effect, the Cu content is preferably 0.01% or more. The Cu content is more preferably 0.02% or more, and further 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 further preferably 0.10% or less.

[0031] Se: 0 to 0.020% Se (selenium) is an element that has a magnetic property improving effect. When Se is contained, the Se content is preferably 0.001% or more in order to effectively exhibit the magnetic property improving effect. The Se content is more preferably 0.003% or more, and further preferably 0.006% or more. On the other hand, if the Se content exceeds 0.020%, the adhesion of the coating film deteriorates. Therefore, the Se content is preferably 0.020% or less. The Se content is more preferably 0.015% or less, and further preferably 0.010% or less.

[0032] Sb: 0 to 0.50% Sb (antimony) is an element that has a magnetic property improving effect. When Sb is contained, in order to effectively exert the magnetic property improving effect, the Sb content is preferably 0.005% or more. The Sb content is more preferably 0.01% or more, and further preferably 0.02% or more. On the other hand, if the Sb content exceeds 0.50%, the adhesion of the coating significantly deteriorates. Therefore, the Sb content is preferably 0.50% or less. The Sb content is more preferably 0.30% or less, and further preferably 0.10% or less.

[0033] As described above, the chemical composition of the base steel sheet of the grain-oriented electrical steel sheet in this embodiment is, for example, one that contains the above-mentioned basic elements with the balance consisting of Fe and impurities, or one that contains the basic elements and further contains one or more other optional elements with the balance consisting of Fe and impurities.

[0034] The chemical composition of the base steel sheet of the grain-oriented electrical steel sheet according to this embodiment can be measured using a known ICP emission spectrometry. The Si content is determined by the method (silicon quantification method) specified in JIS G 1212 (1997). Specifically, when the above-mentioned cutting chips are dissolved in acid, silicon oxide is precipitated, and the precipitate (silicon oxide) is filtered out with filter paper and the mass is measured to determine the Si content. The C content and S content are determined by the well-known high-frequency combustion method (combustion-infrared absorption method). Specifically, the above-mentioned solution is combusted in an oxygen stream by high-frequency heating, and the generated carbon dioxide and sulfur dioxide are detected to determine the C content and S content. The N content is determined using the well-known inert gas fusion-thermal conductivity method. However, when making measurements, if an insulating film is formed on the surface, this must be removed before making measurements. This can be done by immersing the sample in a highly concentrated alkaline solution (e.g., a 30% sodium hydroxide solution heated to 85°C) for 20 minutes or more. Peeling can be determined visually. For small samples, surface grinding may also be used to remove the film.

[0035] <Insulating coating> The grain-oriented electrical steel sheet 100 according to this embodiment has an insulating coating 2 formed on the surface of a base steel sheet 1. The grain-oriented electrical steel sheet 100 according to this embodiment does not have a forsterite-based coating, nor does it have an SiO2 layer as shown in Patent Documents 3 and 4. Therefore, the insulating coating 2 is formed in direct contact with the base steel sheet 1. The insulating coating 2 is made up of an intermediate layer 21 and a tensile coating layer 22 in this order from the base steel sheet 1 side.

[0036] (Middle class) The intermediate layer 21 is a layer (coating) containing a crystalline metal phosphate and having a thickness of 0.3 to 10.0 μm. As described above, grain-oriented electrical steel sheets generally have a forsterite-based coating formed in the final annealing process and an insulating coating (tensile insulating coating) formed thereon. However, in recent years, it has become clear that this forsterite-based coating hinders the movement of domain walls and has a negative effect on iron loss, and thus grain-oriented electrical steel sheets without a forsterite-based coating are being studied in order to further improve magnetic properties. However, in the absence of a forsterite-based coating, it is difficult to ensure sufficient adhesion between the tensile coating and the surface of the base steel sheet.

[0037] In the grain-oriented electrical steel sheet 100 of this embodiment, an intermediate layer 21 containing a crystalline metal phosphate is formed between the base steel sheet 1 and the tensile coating, thereby improving adhesion between the base steel sheet 1 and the tensile coating layer 22 via the intermediate layer 21. When the intermediate layer 21 contains a crystalline metal phosphate, the tensile coating formed thereon (which becomes the tensile coating layer 22 after formation) also contains a metal phosphate, resulting in high affinity and excellent adhesion between the intermediate layer and the tensile coating layer. In addition, when the intermediate layer 21 is formed by immersion in a treatment liquid containing a metal phosphate, as described below, it can be formed on the surface of the base steel sheet 1 by utilizing a chemical reaction, and adhesion between the intermediate layer 21 and the base steel sheet 1 can also be ensured. If the intermediate layer 21 does not contain a crystalline metal phosphate, the above effect cannot be obtained. The ratio of the crystalline metal phosphate in the intermediate layer is preferably 80 mass% or more, more preferably 90 mass% or more, and may be 100 mass%. In terms of adhesion, the metal phosphate is one or more of zinc phosphate, manganese phosphate, iron phosphate, and zinc calcium phosphate. In terms of adhesion to the base steel sheet, the metal phosphate preferably has a total amount (mol) of metal (M) and Fe that is 2.0 times or more, and more preferably 3.0 times or more, the amount of P (mol). It is preferable that the metal phosphate is not a hydrate, since the corrosion resistance decreases when the metal phosphate is a hydrate. In general, the total amount (mol) of the above-mentioned metal (M) and Fe is 1.5 times or less the amount (mol) of P in the hydrate. In the grain-oriented electrical steel sheet according to this embodiment, hydrates inevitably formed during the formation of the intermediate layer may still remain in the end, but the amount is small (usually less than 5.0 mass% of the entire insulating coating 2). From the viewpoint of adhesion, the treatment solution does not contain colloidal silica when the intermediate layer is formed. The remainder of the metal phosphate in the intermediate layer may contain oxides and elements such as Fe and Si diffused from the base steel sheet, but as described above, silica is not intentionally contained, so the Si content is, for example, 1.0 mass% or less. The intermediate layer 21 is formed at a different time from the tensile coating formed thereon, but the intermediate layer 21 and the tensile coating layer 22 together function as the insulating coating 2 .

[0038] The amount (mol) of metal (M), Fe (mol), and P (mol) in the metal phosphate are determined by analyzing a cross section of the insulating coating in the thickness direction using EDS (energy dispersive X-ray spectroscopy). Measurements are performed at about three locations, and the average value is taken as the amount (mol) of each. The amount of hydrate can be roughly determined by measuring the water content by a thermobalance method.

[0039] The average thickness of the intermediate layer 21 is 0.3 to 10.0 μm. If the average thickness of the intermediate layer 21 is less than 0.3 μm, the effect of improving the adhesion between the base steel sheet and the insulating coating via the intermediate layer is insufficient, whereas if the average thickness of the intermediate layer exceeds 10.0 μm, the magnetic properties deteriorate significantly.

[0040] (Tension coating layer) In the grain-oriented electrical steel sheet 100 according to this embodiment, a tensile coating is formed on the surface of the intermediate layer 21, so that a tensile coating layer 22 is provided on the surface side of the insulating coating 2. The tensile coating layer 22 is not particularly limited as long as it is used as an insulating coating for grain-oriented electrical steel sheets, but from the viewpoint of adhesion to the intermediate layer 21 (adhesion to the base steel sheet 1 via the intermediate layer 21), it contains a metal phosphate and silica (derived from colloidal silica in the coating liquid) so that the silica content is 20 mass% or more. On the other hand, if the silica content of the tensile coating layer exceeds 60 mass%, it may cause powdering, so it is set to 60 mass% or less. The tensile coating layer 22 preferably contains at least 70 mass % of metal phosphate and silica in total, and may contain ceramic particles such as alumina and silicon nitride as the remainder other than the metal phosphate and silica. Although the thickness of the tensile coating layer 22 is not limited, the average thickness of the insulating coating 2 (intermediate layer 21 + tensile coating layer 22) is set to 2.0 to 10.0 μm when the average thickness of the intermediate layer 21 is within the above range. If the average thickness of the insulating coating 2 is less than 2.0 μm, sufficient coating tension cannot be obtained. Furthermore, there is a large amount of phosphoric acid eluted. This can cause stickiness and reduced corrosion resistance, and may even cause coating peeling. Furthermore, if the thickness of the insulating coating 2 exceeds 10.0 μm, the space factor can decrease, deteriorating the magnetic properties, or cracks can occur, causing reduced adhesion and reduced corrosion resistance.

[0041] The thickness of the insulating coating 2 is determined by the following method. The cross section of the sample is observed with a scanning electron microscope, and the average thickness can be measured by measuring the thickness at five or more points. Of the insulating coating 2, the intermediate layer 21 and the tensile coating layer 22 can be distinguished by the content of silicon (Si) derived from silica (the tensile coating layer contains silica as described above). Moreover, the average thickness of the insulating coating 2 can be obtained by adding up the average thickness of the intermediate layer 21 and the average thickness of the tensile coating layer 22 .

[0042] In the intermediate layer 21 and the tensile coating layer 22, the mass proportion of the metal phosphate and the type of the metal phosphate can be determined by the following method. Similar to the method for measuring the thickness of intermediate layer 21 and tensile coating layer 22, a scanning electron microscope and an energy dispersive elemental analyzer can be used to identify the mass percentage and type of metal phosphate. Furthermore, whether the metal phosphate of the intermediate layer 21 is a crystalline metal phosphate can be determined by X-ray crystal structure analysis. The silica content of the tensile coating layer 22 can also be measured using a scanning electron microscope and an energy dispersive elemental analyzer.

[0043] <Manufacturing method> The grain-oriented electrical steel sheet according to the present embodiment can be suitably manufactured by a manufacturing method that satisfies the manufacturing conditions described below. However, the grain-oriented electrical steel sheet according to the present embodiment is not limited to a particular manufacturing method. In other words, the grain-oriented electrical steel sheet having the above-mentioned configuration is considered to be the grain-oriented electrical steel sheet according to the present embodiment, regardless of its manufacturing conditions.

[0044] The grain-oriented electrical steel sheet according to this embodiment is (I) a hot rolling step of hot rolling a steel slab having a predetermined chemical composition to obtain a hot rolled sheet; (II) a hot-rolled sheet annealing step of annealing the hot-rolled sheet; (III) a cold rolling step in which the hot-rolled sheet after the hot-rolled sheet annealing step is cold-rolled to obtain a steel sheet (cold-rolled sheet); (IV) a decarburization annealing step of performing decarburization annealing on the steel sheet after the cold rolling step; (V) a finish annealing step of applying an annealing separator containing 10 to 100 mass% of Al2O3 to the steel sheet after the decarburization annealing step, drying the steel sheet, and then performing finish annealing; (VI) an annealing separator removing step of removing excess annealing separator from the steel sheet after the final annealing step; (VII) an immersion step of immersing the steel sheet after the annealing separator removal step in a treatment solution having a liquid temperature of 40 to 85° C. and containing 5 to 50 mass % of a metal phosphate for 5 to 150 seconds; (VIII) a drying step of removing the steel sheet after the immersion step from the treatment solution, removing excess of the treatment solution, and then drying the steel sheet; (IX) a tensile coating layer forming step of applying a coating liquid containing a metal phosphate and colloidal silica in an amount of 30 to 150 parts by mass of colloidal silica per 100 parts by mass of the metal phosphate to the steel sheet after the drying step, drying the steel sheet, and then maintaining the steel sheet at a sheet temperature of 700 to 950°C for 10 to 120 seconds; The composition can be produced by a production method including the steps of: In addition, the method for producing the grain-oriented electrical steel sheet according to this embodiment further includes the steps of: (X) a nitriding process for performing a nitriding process on the steel sheet between the decarburization annealing process and the finish annealing process; (XI) a magnetic domain refining step for controlling magnetic domains of the steel sheet after the tensile coating layer forming step; may include either or both of the following: In addition, the method for producing a grain-oriented electrical steel sheet according to this embodiment further includes the steps of: (XII) a surface conditioning step for controlling the reactivity of the surface of the steel sheet; may also include. Of these, the characteristic steps in the production of the grain-oriented electrical steel sheet according to this embodiment are the steps (V) finish annealing step to (IX) tensile coating layer formation step, which are mainly related to the formation of the insulating coating, and for the other steps or conditions not described, publicly known conditions can be adopted. These steps will be described below.

[0045] <Hot rolling process> In the hot rolling process, a steel billet such as a slab having a predetermined chemical composition is heated and then hot rolled to obtain a hot-rolled sheet. The heating temperature of the steel billet is preferably within a range of 1100 to 1450°C. The heating temperature is more preferably 1300 to 1400°C. The chemical composition of the steel slab may be changed depending on the chemical composition of the grain-oriented electrical steel sheet that is ultimately to be obtained, but an example of a chemical composition may include, in mass%, C: 0.01-0.20%, Si: 2.50-4.00%, sol. Al: 0.01-0.040%, Mn: 0.01-0.50%, N: 0.020% or less, S: 0.005-0.040%, Cu: 0-0.50%, Sn: 0-0.50%, Se: 0-0.020%, Sb: 0-0.50%, and the balance being Fe and impurities. The hot rolling conditions are not particularly limited and may be appropriately set based on the desired properties. The thickness of the hot rolled sheet is preferably within a range of, for example, 2.0 mm to 3.0 mm.

[0046] <Hot-rolled sheet annealing process> The hot-rolled sheet annealing process is a process of annealing the hot-rolled sheet manufactured through the hot rolling process. By carrying out such an annealing treatment, recrystallization occurs in the steel sheet structure, and it is possible to realize good magnetic properties, which is preferable. When hot-rolled sheet annealing is performed, the hot-rolled sheet produced through a hot rolling process 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. The annealing conditions are also not particularly limited. For example, the hot-rolled sheet may be annealed in a temperature range of 900 to 1200°C for 10 seconds to 5 minutes.

[0047] <Cold rolling process> In the cold rolling process, the hot rolled sheet after the hot rolled sheet annealing process is subjected to cold rolling to obtain a steel sheet (cold rolled sheet). The cold rolling may be a single cold rolling (a series of cold rolling without annealing in between), or may be multiple cold rolling passes with intermediate annealing between them, with the cold rolling being interrupted and at least one or two or more intermediate annealing passes being performed before the final pass of the cold rolling process. When intermediate annealing is performed, it is preferable to hold the steel sheet at a temperature of 1000 to 1200° C. for 5 to 180 seconds. The annealing atmosphere is not particularly limited. In consideration of the manufacturing cost, it is preferable to perform intermediate annealing three times or less. Furthermore, the surface of the hot-rolled sheet may be subjected to pickling before the cold rolling step.

[0048] In the cold rolling step according to the present embodiment, the hot rolled sheet after the hot rolled sheet annealing step may be cold rolled to obtain a steel sheet according to a known method. For example, the final rolling reduction may be within a range of 80 to 95%. If the final rolling reduction is 80% or more, the {110} <001> This is preferable because Goss nuclei having a high degree of orientation in the rolling direction can be obtained. On the other hand, if the final rolling reduction exceeds 95%, it is not preferable because the secondary recrystallization is likely to become unstable in the subsequent finish annealing process. 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.

[0049] <Decarburization annealing process> In the decarburization annealing step, the obtained steel sheet is subjected to decarburization annealing. In the decarburization annealing, the conditions of the decarburization annealing are not limited as long as the steel sheet is subjected to primary recrystallization and C, which adversely affects magnetic properties, can be removed from the steel sheet. For example, the oxidation degree (PH2O / PH2) in the annealing atmosphere (furnace atmosphere) is set to 0.3 to 0.6, and the annealing temperature is set to 800 to 900°C for 10 to 600 seconds.

[0050] <Nitriding process> A nitriding treatment may be carried out between the decarburization annealing step and the finish annealing step described below. In the nitriding process, for example, the steel sheet after the decarburization annealing process is maintained at about 700 to 850°C in a nitriding atmosphere (an atmosphere containing hydrogen, nitrogen, and ammonia or other gases having nitriding ability) to perform nitriding. When AlN is used as an inhibitor, it is preferable that the N content of the steel sheet after the nitriding process is 40 ppm or more by the nitriding process. On the other hand, if the N content of the steel sheet after the nitriding process exceeds 1000 ppm, excessive AlN remains in the steel sheet even after the completion of secondary recrystallization in the finish annealing. Such AlN causes iron loss deterioration. For this reason, it is preferable that the N content of the steel sheet after the nitriding process is 1000 ppm or less.

[0051] <Finish annealing process> In the final annealing process, an annealing separator containing 10 to 100 mass % of Al2O3 is applied to the steel sheet after the decarburization annealing process or after the nitriding process (after the nitriding process), dried, and then final annealing is performed. In conventional manufacturing methods for grain-oriented electrical steel sheets, an annealing separator mainly composed of MgO is applied and finish annealing is performed to form a forsterite-based coating on the surface of the steel sheet (cold-rolled sheet). In contrast, in the manufacturing method for grain-oriented electrical steel sheet according to the present embodiment, an annealing separator containing Al2O3 is used so as not to form a forsterite-based coating. On the other hand, the proportion of Al2O3 may be 100% by mass, but from the viewpoint of preventing Al2O3 from seizing onto the steel sheet surface, in the manufacturing method of grain-oriented electrical steel sheet according to this embodiment, it is preferable that the annealing separator contains MgO. The content of MgO may be 0%, but in order to obtain the above effect, the proportion of MgO is preferably 5% by mass or more. If MgO is contained, the proportion of MgO is 90% by mass or less to ensure 10% by mass or more of Al2O3. The proportion of MgO is preferably 50% by mass or less. In the method for producing a grain-oriented electrical steel sheet according to the present embodiment, the annealing separator may further contain a chloride. When the annealing separator contains a chloride, an effect is obtained in which a forsterite-based coating is more unlikely to be formed. The chloride content is not particularly limited and may be 0%, but in order to obtain the above effect, a content of 0.5 to 10 mass% is preferable. As the chloride, for example, bismuth chloride, calcium chloride, cobalt chloride, iron chloride, nickel chloride, etc. are effective. The finish annealing conditions are not limited, but may be, for example, a condition in which the steel sheet is held at a temperature of 1150 to 1250° C. for 10 to 60 hours.

[0052] <Annealing separator removal process> After the final annealing step, excess annealing separator is removed from the steel sheet. For example, the excess annealing separator can be removed by washing with water.

[0053] <Surface conditioning process> A surface conditioning step for controlling the reactivity of the surface of the steel sheet may be carried out between the annealing separator removal step and the immersion step. The conditions for the surface conditioning step are not limited, but an example of the conditions is that the steel sheet after the annealing separator removal step is immersed in a commercially available surface conditioning agent for 30 seconds to 1 minute.

[0054] <Soaking process> <Drying process> The steel sheet after the annealing separator removal step (or after a surface conditioning step, if necessary) is immersed in a treatment solution containing 5 to 50 mass% of a specified metal phosphate at a liquid temperature of 40 to 85°C for 5 to 150 seconds (immersion step). Thereafter, the steel sheet is pulled out of the treatment solution, and the excess treatment solution is removed, followed by drying (drying step). As a result, an intermediate layer containing a crystalline metal phosphate is formed on the surface of the steel sheet (base steel sheet). If the liquid temperature is less than 40° C. or the immersion time is less than 5 seconds, an intermediate layer with sufficient thickness cannot be obtained. On the other hand, if the liquid temperature is more than 85° C. or the immersion time is more than 150 seconds, the intermediate layer will be excessively thick. If the metal phosphate content in the treatment solution is less than 5% by mass, the formation of the intermediate layer will be slow, resulting in high industrial costs.To achieve a uniform thickness for the intermediate layer, the metal phosphate content is preferably 10% by mass or more. On the other hand, if the metal phosphate exceeds 50% by mass, the crystal grains may become coarse, which may cause a decrease in adhesion. The metal phosphate contained in the treatment liquid may be one or more of zinc phosphate, manganese phosphate, and zinc calcium phosphate. In addition, if the drying temperature is high, voids may occur and adhesion may be deteriorated, so the drying temperature is preferably 300° C. or less, and more preferably 200° C. or less. The drying temperature is preferably 100° C. or more.

[0055] <Tension film layer formation process> In the tensile coating layer formation process, a coating liquid containing a metal phosphate and colloidal silica is applied to the steel sheet after the drying process (steel sheet with an intermediate layer formed on the base steel sheet), dried, and then held at a sheet temperature of 700 to 950° C. for 10 to 120 seconds to form a tensile coating. The layer made of this tensile coating (tensile coating layer 22) and the intermediate layer 21 form the insulating coating 2. If the sheet temperature during holding is less than 700°C, the tension will be low and the magnetic properties will be inferior. Therefore, it is preferable to set the sheet temperature to 700°C or higher. On the other hand, if the sheet temperature exceeds 950°C, the rigidity of the steel sheet will decrease and it will be easily deformed. In this case, the steel sheet may be distorted due to transportation, etc., and the magnetic properties may be inferior. Therefore, it is preferable to set the sheet temperature to 950°C or lower. Moreover, if the retention time is less than 10 seconds, the dissolution property becomes poor. Therefore, the retention time is set to 10 seconds or more. On the other hand, if the retention time exceeds 120 seconds, the productivity becomes poor. Therefore, the retention time is preferably 120 seconds or less. The coating liquid contains a metal phosphate and colloidal silica in an amount of 30 to 150 parts by mass per 100 parts by mass of the metal phosphate. As the metal phosphate, for example, one or a mixture of two or more selected from aluminum phosphate, zinc phosphate, magnesium phosphate, nickel phosphate, copper phosphate, lithium phosphate, cobalt phosphate, etc. can be used. The coating liquid may contain additional elements such as vanadium, tungsten, molybdenum, zirconium, etc. When these elements are contained, they can be added to the coating liquid as, for example, an oxygen acid. Colloidal silica can be of type S or type C. Type S colloidal silica refers to a silica solution that is alkaline, while type C colloidal silica refers to a silica solution in which the silica particle surface is aluminum-treated and the silica solution is alkaline to neutral. Type S colloidal silica is widely used and is relatively inexpensive, but it must be careful when mixed with an acidic metal phosphate solution as it may aggregate and precipitate. Type C colloidal silica is stable even when mixed with a metal phosphate solution and there is no risk of precipitation, but it is relatively expensive due to the large number of processing steps. It is preferable to use them according to the stability of the coating liquid to be prepared.

[0056] <Magnetic domain refining process> The method for producing a grain-oriented electrical steel sheet according to this embodiment may further include a magnetic domain refining step of subjecting the steel sheet after the tensile coating layer forming step to magnetic domain refining. By performing magnetic domain refining treatment, it is possible to further reduce the core loss of grain-oriented electrical steel sheet. Methods of magnetic domain subdivision include a method of narrowing the width of 180° magnetic domains (subdividing 180° magnetic domains) by forming linear or dot-like grooves extending in a direction intersecting the rolling direction at specified intervals along the rolling direction, and a method of narrowing the width of 180° magnetic domains (subdividing 180° magnetic domains) by forming linear or dot-like stress distortion portions or grooves extending in a direction intersecting the rolling direction at specified intervals along the rolling direction. In the case of forming the stress-strained portion, laser beam irradiation, electron beam irradiation, etc. can be applied. In addition, in the case of forming the groove portion, a mechanical groove forming method using gears, etc., a chemical groove forming method in which a groove is formed by electrolytic etching, and a thermal groove forming method using laser irradiation can be applied. In cases where damage occurs to the insulating coating due to the formation of stress-distorted portions or grooves, causing deterioration of properties such as insulation, the insulating coating may be formed again to repair the damage. EXAMPLES

[0057] A slab containing, in mass%, C: 0.08%, Si: 3.29%, sol. Al: 0.028%, N: 0.008%, Mn: 0.15%, S: 0.007%, and the remainder being Fe and impurities was cast. The slab was heated to 1350° C. and then hot rolled to form a hot-rolled sheet having a thickness of 2.2 mm. This hot-rolled sheet was annealed at 1100° C. for 10 seconds (hot-rolled sheet annealing), and then cold-rolled to a sheet thickness of 0.22 mm to obtain a steel sheet (cold-rolled sheet). This steel sheet was subjected to decarburization annealing at 830°C for 90 seconds in an atmosphere with a (PH2O / PH2) ratio of 0.4. Then, except for No. 127, an annealing separator containing 48 mass% Al2O3, 48 mass% MgO, and 4 mass% bismuth chloride was applied to the steel sheets, dried, and then final annealed at 1200°C for 20 hours. For No. 127, an annealing separator consisting of only Al2O3 (100 mass%) was applied to the steel sheet, dried, and then final annealed at 1200°C for 20 hours.

[0058] When the excess annealing separator was removed from the steel sheet after the final annealing step by rinsing with water, it was found that no forsterite-based film had been formed on the surface of the steel sheet. This steel sheet was immersed in a treatment solution shown in Table 1, and then heated to 100 to 150° C. and dried to form an intermediate layer (any of intermediate layers No. 1 to 10). The average thickness of the intermediate layer was as shown in Table 1. X-ray crystal structure analysis showed that the metal phosphates in intermediate layers No. 1 to No. 9 were all crystalline metal phosphates. In these crystalline metal phosphates, the ratio of the total amount (mol) of metal (M) and Fe to the amount (mol) of P was approximately 2:1 or 3:1. No. 10 metal phosphate (magnesium phosphate) was not a crystalline metal phosphate.

[0059] [Table 1]

[0060] Steel sheets (No. 101 to 127) on which various intermediate layers were formed were cut into several pieces as necessary, and coating liquid containing metal phosphate and colloidal silica shown in Table 2 was applied to each steel sheet, and the steel sheets were baked in a drying oven for the time shown in Table 2 so that the sheet temperature in Table 2 was reached, forming a tensile coating on the surface. When vanadium, tungsten, molybdenum, or zirconium was contained in the coating liquid, it was added as an oxyacid (V2O4, WO3, MoO3, ZrO2) in the molar ratio shown in Table 2. When forming the tensile coating layer, the thickness was changed by changing the amount of coating liquid applied. Some of the coating liquids contained alumina or silicon nitride as the remainder. In this way, steel sheets (grain-oriented electrical steel sheets) were manufactured.

[0061] For the obtained steel sheets (Nos. 101 to 127), the silica and metal phosphate contents in the tensile coating layer and the average thickness of the insulating coating were determined by the methods described above. The results are shown in Table 2. In addition, the chemical composition of the base steel plate was investigated and found to contain Si: 3.28%, C: 0.001%, sol. Al: less than 0.001%, N: 0.001%, Mn: 0.07%, S: less than 0.0005%, with the remainder being Fe and impurities.

[0062] [Table 2]

[0063] The adhesion, coating tension, corrosion resistance, elution, and magnetic properties of the insulating coating were measured for these steel sheets using the methods described below. The results are shown in Table 3.

[0064] [Adhesion] The adhesion of the coating was evaluated by taking a sample of 30 mm width and 300 mm length from the steel plate, subjecting this sample to stress relief annealing at 800°C for 2 hours in a nitrogen flow, and then winding it around a 10 mmφ cylinder and unwinding it to a bending adhesion test, after which the degree of peeling of the coating (area ratio) was measured. The evaluation criteria were as follows, and a rating of A or B was determined to indicate excellent coating adhesion. A: Peeling area rate 0-0.5% B: Peeling area rate more than 0.5%, less than 5.0% C: Peeling area ratio more than 5.0%, less than 20% D: Peeling area ratio more than 20%, less than 50% E: Peeling area rate over 50%

[0065] [Coating tension] The coating tension was calculated by taking a sample from the steel plate and working backwards from the state of curvature when the insulating coating on one side of the sample was peeled off. When the obtained film tension was 4.0 MPa or more, it was judged that the film tension was excellent.

[0066] [Corrosion resistance] In accordance with the salt spray test of JIS Z2371:2015, a 5% NaCl aqueous solution was allowed to fall naturally onto the sample for 7 hours in a 35°C atmosphere. The rusted area was then evaluated on a 10-point scale. The evaluation criteria were as follows, and a score of 5 or more (5 to 10) was judged to be excellent in corrosion resistance. 10: No rust occurred 9: Very little rust (area rate 0.1% or less) 8: Area ratio of rusted surface = 0.1% to 0.25% 7: Area ratio of rusted surface = 0.25% to 0.50% 6: Area ratio of rusted surface = over 0.50% and 1% or less 5: Area ratio of rusted surface area = 1% to 2.5% 4: Area ratio of rusted surface: over 2.5% and 5% or less 3: Area ratio of rusted surface = over 5% and 10% or less 2: Area ratio of rusted surface = 10% to 25% 1: Area ratio of rusted surface = 25% to 50%

[0067] [Dissolution] Samples were taken from the obtained steel sheets, and the samples were boiled in boiling pure water for 10 minutes, and the amount of phosphoric acid dissolved in the pure water was measured. The amount of phosphoric acid dissolved was divided by the area of ​​the insulating coating of the boiled grain-oriented electrical steel sheet to obtain the elution rate (mg / m 2 ) was evaluated. The amount of phosphoric acid dissolved in the pure water was measured by cooling the pure water (solution) into which the phosphoric acid had dissolved, and then diluting the cooled solution with pure water to obtain a sample, and measuring the phosphoric acid concentration of the resulting sample using ICP-AES. The amount of elution per unit area is 140mg / m 2 If the value was less than this, it was determined that the dissolution property was excellent.

[0068] [Magnetic properties] The iron loss was evaluated as a magnetic property. Specifically, the obtained steel sheet was irradiated with UA (irradiation energy density) of 2.0 mJ / mm 2 The magnetic domain refinement process was performed by irradiating a laser beam under the above conditions, and the iron loss after the magnetic domain refinement process (iron loss W17 / 50 at 50 Hz and 1.7 T) was measured. If the iron loss was 0.70 W / kg or less, it was determined that the magnetic properties were excellent.

[0069] [Table 3]

[0070] As shown in Tables 1 to 3, Nos. 101 to 115 and 127, which are examples of the present invention, were excellent in coating adhesion, coating tension and magnetic properties. In addition, the corrosion resistance and elution properties were also sufficient. In contrast, Nos. 116 to 126 were poor in at least one of the coating adhesion, coating tension and magnetic properties. In addition, there were cases where the corrosion resistance and elution properties were also poor. [Explanation of symbols]

[0071] 1 Base steel plate 2. Insulation coating 21 Middle Class 22 Tension coating layer 100 grain-oriented electrical steel sheet

Claims

1. A base steel plate; An insulating coating formed on a surface of the base steel sheet; having The insulating coating is An intermediate layer formed on the base steel sheet side and containing a crystalline metal phosphate; a tensile coating layer formed on a surface side of the insulating coating, The average thickness of the intermediate layer is 0.3 to 10.0 μm, The average thickness of the insulating coating is 2.0 to 10.0 μm; The crystalline metal phosphate of the intermediate layer is one or more of zinc phosphate, manganese phosphate, iron phosphate, and zinc calcium phosphate, the crystalline metal phosphate is not a hydrate, The tensile coating layer contains a metal phosphate and silica, and the content of the silica in the tensile coating layer is 20 to 60 mass %. The grain-oriented electrical steel sheet is characterized in that

2. A method for forming the insulating coating provided on the grain-oriented electrical steel sheet according to claim 1, comprising the steps of: Steel plate, Al ２ O ３ A finish annealing process in which an annealing separator containing 10 to 100 mass% of the above is applied, dried, and then finish annealed; an annealing separator removing step of removing excess annealing separator from the steel sheet after the finish annealing step; an immersion step of immersing the steel sheet after the annealing separator removal step in a treatment solution having a liquid temperature of 40 to 85° C. and containing 5 to 50 mass % of a metal phosphate for 5 to 150 seconds; a drying step of removing the steel sheet after the immersion step from the treatment liquid, removing excess of the treatment liquid, and then drying the steel sheet; a tensile coating layer forming step of applying a coating liquid containing a metal phosphate and colloidal silica in an amount of 30 to 150 parts by mass of colloidal silica per 100 parts by mass of the metal phosphate to the steel sheet after the drying step, drying the steel sheet, and then maintaining the steel sheet at a sheet temperature of 700 to 950° C. for 10 to 120 seconds; Equipped with A method for forming an insulating coating comprising the steps of:

3. The annealing separator further contains one or more of MgO: 5 to 90 mass% and chloride: 0.5 to 10.0 mass%; 3. The method for forming an insulating coating according to claim 2.

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