TW200525042A - Method for annealing grain oriented magnetic steel sheet and method for producing grain oriented magnetic steel sheet - Google Patents

Abstract

This invention relates to a method for annealing a grain oriented magnetic steel sheet, in which a treating fluid containing an Al compound in the form of a solution or a colloidal solution and further a compound stable at a high temperature and having a viscosity of 25 mPa s or less is used as an separation agent for annealing. The separating agent exhibits good separation effect for annealing without the occurrence of powdery dust problems and of the staining of a production line. A method for producing a grain oriented magnetic steel sheet, in which the above separation agent for annealing is applied to a finish annealing step and the like. The method allows the production of a grain oriented magnetic steel sheet which has no forsterite-like coating film or is excellent in characteristics of a forsterite-like coating film.

Description

200525042 IX. Description of the invention: [Technical field to which the invention belongs] The present invention relates to an annealing release agent that prevents directional steel plates from fusing to each other during annealing, and an annealing method using the annealing release agent. The present invention also relates to a method for manufacturing a grain-oriented electrical steel sheet using the annealing separator. Here, the directional electromagnetic steel sheet includes those having a forsterite film and those without a forsterite film, and the present invention relates to a method for manufacturing each of them. [Previous technology] Electromagnetic steel plates are materials widely used as core materials for transformers or rotating machines. Among them, the directional electromagnetic steel sheet is a steel sheet having a high iron loss due to the highly integrated crystalline azimuth in the {1 1 0 丨 < 0 0 1 > azimuth called a Gaussian azimuth. Among the characteristics required for electromagnetic steel plates, especially the iron loss characteristics are characteristics directly related to the energy loss of the product, so they are valued. Also, in the electromagnetic steel sheet, punchability (p u n c h a b i 1 i t y) or bending workability are also important characteristics. That is, in the case of manufacturing the core of a transformer or a rotating machine, the electromagnetic steel sheet is formed into a predetermined shape by processing such as punching, cutting, and bending. In addition, when the steel strip passes through the processing lines for such processing, the steel sheet is bent. Therefore, the above characteristics are important. In general, the grain-oriented electrical steel sheet is manufactured using steps disclosed in, for example, paragraph [0 0 5] of Japanese Patent Laid-Open Nos. 2 0-4 1 3 2 3. That is, the steel sheet obtained by rolling (r ο 1 1 i n g) is subjected to recrystallization annealing, and then subjected to a batch annealing called a post-processing (f i n i s h i n g) annealing. By this batch annealing, secondary recrystallization is promoted to achieve the knot of the Da Gaussian orientation. 3 12XP / Invention Specification (Supplement) / 94-03 / 93137129 200525042 Grain accumulation. Secondly, in batch annealing, steel plates are heated in a coil shape, but batch annealing for manufacturing directional electromagnetic steel plates generally needs to be at a high temperature, and therefore, the steel plates are dazzled with each other in the coil. In order to prevent such fusing, the technique of coating an annealing separator containing MgO as a main component and forming a magnesite stone film during annealing is widely used. The forsterite film is considered to be a film formed by the reaction between MgO in the annealing separator and S i 0 2 in the oxide formed on the surface of the steel sheet (but the film also contains Fe). This forsterite film has good annealing and separation properties, and it also has one side that is beneficial to the characteristics of the grain-oriented electrical steel sheet. For example, a hard coat (tensile film) can be imparted to the forsterite film with good adhesion, so that the steel sheet can be tensioned, and iron loss can be reduced. Conversely, since the forsterite film is a kind of hard glass film, the grain-oriented electrical steel sheet with forsterite film is not good in punchability or bending workability. That is, there is a problem that the punching die is rapidly worn, or a burr (b u r r) occurs on the cut surface of the steel plate. In addition, since peeling easily occurs during bending processing, good bending and peeling resistance is required, and it does not peel even when processing such as bending is applied after relaxation annealing. In order to solve these problems, the proposals are as follows: (1) As a means to obtain a grain-oriented electrical steel sheet with good workability (emphasis on workability), a method of manufacturing a grain-oriented electrical steel sheet without forming a forsterite film that is not detrimental to the workability itself. Methods; and (2) attaching importance to low iron loss, etc., to form a magnesium mullite 6 312XP / manufacturing specification (Supplementary Specification) which has good resistance to bending and peeling even if processed by bending or the like after relaxation annealing, and will not peel off. Pieces) / 94-03 / 93] 37129 200525042 method of coating. As the method of (1), the method of changing the composition of the annealing release agent is to apply an annealing release agent that does not contain M g 0 that reacts with S i 0 2 on the surface of the steel plate after recrystallization annealing, and apply it. A process annealing method is tried. Here, as an annealing separator containing a component other than MgO as a main component, Japanese Patent Laid-Open No. 6-1 3 6 4 4 8, Japanese Patent Laid-Open No. 7-1 1 8 7 50, and Japanese Patent Laid-Open No. Hei 6 are known. 5-1 5 6 3 6 The annealed separating agent containing alumina (powder) as the main ingredient disclosed in Japanese Patent Publication No. JP 6-2 1 6 and Japanese Patent Publication No. 8-1 3 4 5 4 An annealing and separating agent based on alumina and / or silicon dioxide as disclosed in the No. 2 bulletin. These annealing and separating agents are applied to the steel sheet by electrostatic coating or as a suspension in which an aqueous slurry (s 1 u r r y) or alcohol is suspended. However, these annealed release agents are susceptible to peeling in the through-plate of the manufacturing line after the annealing release agent is applied due to the lack of adhesion to the steel sheet. Therefore, there are the following problems: 1) it is difficult to control the coating amount; 2) the yield of the annealed release agent is not good; 3) dust may be generated and contamination of the production line may be caused due to this. As an annealing release agent with excellent adhesion to steel plates, an annealing release agent based on a colloidal alumina aggregate in the form of feathers is disclosed in Japanese Patent Laid-Open No. 1 0 _ 1 2 1 1 4 2 Bulletin. However, the problem with this annealed release agent is that it is difficult to uniformly coat the steel sheet. In addition, before further forming the insulating film, the annealing and separating agent must be subjected to a removal step using pickling or inspection cleaning, which causes inconvenience in operation. In short, once the forsterite film is formed in the conventional technology, the forsterite is removed by means of pickling, chemical grinding, or electrolytic grinding. 93137129 200525042 Such a costly and complicated method of coating has been implemented as the most practical method. In addition, attempts have been made to produce a grain-oriented electrical steel sheet with good processability without using an annealing separator. For example, Japanese Patent Laid-Open No. 2000- 1 2 9 3 5 6 proposes a technique for re-crystallizing Gaussian orientation crystal grains by using a component that does not contain an inhibitor-forming component, and considers it possible to borrow This method lowers the post-processing annealing temperature and eliminates the need for an annealing separator. However, although the annealing of the grain-oriented electrical steel sheet after processing belongs to a low temperature, it is not a level that can completely prevent the steel sheet from being welded, and there are still problems from the viewpoint of stable production. On the other hand, as a method of (2), the above-mentioned Japanese Patent Laid-Open No. 2 0 3 _ 4 1 3 2 3 discloses a batch method in which continuous annealing is performed twice after recrystallization annealing. Annealing is a technique to achieve both magnetic characteristics and film characteristics. That is, in the conventional technique, the secondary recrystallization and the formation of the forsterite film have been achieved in the post-processing annealing. However, since the optimal annealing conditions are not consistent between the two sides, if the magnetic properties are to be improved, the film characteristics may be deteriorated. If the magnetic properties are to be improved, the magnetic characteristics may be deteriorated. In this regard, the technology disclosed in Japanese Patent Laid-Open No. 2000- 4 1 3 2 3 is to try to achieve the function of post-processing annealing by using two batch annealing, that is, using the first batch annealing to Promote secondary recrystallization, and use the second batch annealing to form a magnesite-like stone film. In this publication, it is considered that in the first batch annealing, it is possible that the steel plates are closely adhered to each other, and an annealing release agent may also be applied. However, in the first batch annealing after recrystallization annealing, if MgO is used as the main annealing separator 8 312XP / Invention Specification (Supplement) / 94-03 / 93〗 37129 200525042, the The formation of the forsterite film in the secondary batch annealing has a bad influence, and it becomes very difficult to obtain good film characteristics. Further, in the method of the above-mentioned Japanese Patent Laid-Open No. 2003- 4 1 3 2 3, it is preferable to perform decarburization after the first batch annealing, but a film such as a forsterite film There are also disadvantages that hinder decarbonization. On the other hand, if the first batch annealing is performed without using an annealing separator containing MgO as a main component, the same problems as in (1) are caused. [Summary of the Invention] (Problems to be Solved by the Invention) The present invention is proposed by the present invention to solve the above problems, and proposes a method that does not contain M g 0, and has excellent coating properties and adhesiveness after coating. Annealing and separating agent for manufacturing directional electromagnetic steel sheet without causing dust problem and pollution of production line and annealing method using the annealing and separating agent. The present invention also relates to a method for manufacturing a grain-oriented electrical steel sheet suitable for a core material of a transformer or a rotary machine using the annealing separator. In particular, the present invention proposes a method for manufacturing a directional electromagnetic steel sheet having excellent coating characteristics of a forsterite film and a directional electromagnetic steel sheet having no forsterite coating, a film, and excellent processability. (Means for solving problems) The form of the present invention can be classified into: (1) an annealing method of a grain-oriented electromagnetic steel sheet; (2) the use as an annealing separating agent; (3) a grain-oriented electrical steel sheet having a magnesite-like film Manufacturing method; and (4) a manufacturing method of a grain-oriented electrical steel sheet without a forsterite film. (1) Annealing method for steel sheet 9 3 12XP / Invention Specification (Supplement) / 94-03 / 93137129 200525042 The present invention is an annealing method for directional electromagnetic steel sheet, which is an annealing separator coated on the steel sheet and coated. For an annealed steel sheet, the above-mentioned annealing separating agent contains an A 1 compound in the state of a solution or a colloid (c ο 1 1 〇id) solution, and contains a compound stable at high temperature, and further has a viscosity of 25 m Pa · s or less. By. Preferably, after the application of the annealing separator, the baking treatment is performed by baking the annealing separator. Here, a compound that is stable at a high temperature refers to a compound that does not or does not easily react with the surface of a steel plate or an oxide on the surface of a steel plate when the target is annealed, and that the compound itself does not occur or is difficult to react. Specifically, at least one selected from the group consisting of a Si compound, a Sr compound, a Ca compound, a Zr compound, a Ti compound, and a Ba compound can be exemplified. In addition, although MgO is stable at high temperatures alone, it reacts with oxides on the surface of the steel sheet, so it does not meet the "stability at high temperatures" referred to here. Here, since the A 1 compound is in a solution state or a colloidal solution state, it is a structural part (functional group, etc.) having an affinity for a liquid (for convenience, collectively referred to as a solvent) for forming a solution or a colloidal solution. substance. Therefore, it is a substance which is chemically different from, for example, alumina particles used in a general slurry or suspension. Moreover, it is different from a slurry or a suspension in terms of existence, and it goes without saying. The solvent is preferably water based. In addition, the A 1 compound is preferably at least any one of a dehydration reaction product (also including a partially dehydrated reaction product) of the A 1 compound having a hydroxyl group and an organic acid group, and the A 1 compound having a hydroxyl group and an organic acid group. / Invention Specification (Supplement) / 94-03 / 93137129 200525042. It is further preferred that the A 1 compound is selected from the group consisting of acetic acid A 1, acetic acid A 1, chloric acid A 1, nitro acid A 1, oxalic acid A 1, and amine amino acid A 1 1. One or more mixtures of lactic acid A 1 and citric acid A 1. In addition, the annealing separator may contain a compound which is stable at a high temperature in a state of a solution or a colloidal solution. The content of the A 1 compound is preferably a solid content ratio of 40 to 95 mass% represented by the following formula (1). Solid content ratio of A 1 compound = (solid content of the above A 1 compound) / {(solid content of the above A 1 compound) + (solid content (and) of the compound stable at the above-mentioned high temperature) 丨 ... formula (1) but The solid component of the above-mentioned A 1 compound is converted into A 1 2 0 3, and the stable compound at the above-mentioned high temperature is converted into a main compound produced in the case of baking after the above-mentioned annealing separating agent is applied. The present invention is preferably an annealing method for a directional electromagnetic steel sheet, which is an annealing separator coated on a steel sheet and the coated steel sheet, the annealing separator contains an A 1 compound in the state of a solution or a colloidal solution, And further contains at least one compound selected from the group consisting of a Si compound, a Sr compound, a Ca compound, a Zr compound, a Ti compound, and a Ba compound, and the content of the A1 compound is represented by the following formula (2) The solid content ratio shown is 40 to 95 mass%, and the viscosity of the annealing separator is 25 mPa · s or less. Here, the solid content ratio of the A 1 compound = (solid content of the A 1 compound) / {(solid content of the A 1 compound) + (solid content (and) of at least one of the above compounds) 丨 ... (2) 11 312XP / Invention specification (Supplement) / 94-03 / 93137129 200525042 Here, the solid content of each compound is converted to the value of the weight of each of the following compounds: A1 compound ·· AI2O3; Si compound ··· 5ί〇2;

Sr compounds ... SrO; Ca compounds ... CaO; Z r compounds ... Z r〇2; Ti compounds ... Ti〇2;

Ba compound " -BaO. Here, the annealing separating agent may contain at least one compound selected from the group consisting of the above-mentioned Si compound, S r compound, Ca compound, Z r compound, T i compound, and Ba compound in the state of a solution or a colloidal solution. . A particularly suitable form of the invention is an annealing method for a grain-oriented electrical steel sheet. An annealing separator is coated on the steel sheet, and the coated steel sheet is annealed by the above-mentioned annealing separator. The compounds are A 1 compounds and Si compounds. As the main component, the ratio of the A 1 compound to the Si compound is converted into A 1 2 0 3 / (A 1 2 0 3 + Si〇2). The value is 40 ~ 95 mass%, the viscosity is 25 mPa · s or less, and it is a solution. Or the state of a colloidal solution. In the above invention, the annealing separating agent may further contain S or an S-containing compound at 25 to n ass% at a solid content ratio determined in the case where the annealing separating agent is applied and baked. The "S or S-containing compound" is preferably at least one selected from the group consisting of sulfuric acid Sr, sulfuric acid Mg, and sulfurized Mg. (2) Use as an annealing separating agent The present invention is the use of a liquid as an annealing separating agent. The liquid system contains an A 1 compound in a state of a solution 'or a colloidal solution, and further contains a compound selected from Si compounds, S r compounds, For at least one compound in the group consisting of C a compound, Z r compound, T i compound, and B a compound, the content of the above-mentioned A 1 12 312XP / Invention Specification (Supplement) / 94-03 / 93137129 200525042 is based on the above formula (2) The solid content ratio shown is 40 to 95 in ass%, and the viscosity is 25 m Pa · s or less. Here, the annealing separating agent may contain at least one compound selected from the group consisting of the above-mentioned Si compound, S r compound, Ca compound, Z r compound, T i compound, and Ba compound in the state of a solution or a colloidal solution. . The invention also uses a liquid as an annealing separator. The liquid system mainly uses A 1 compound and S i compound, and the ratio of A 1 compound and S i compound is converted into Al2OJ (Al2〇3 + Si〇2 The value of) is 40 to 95 mass%, the viscosity is 25 mPa · s or less, and the state is a solution or a colloidal solution. In addition, the annealing separator suitable for the annealing method of the steel plate described in (1) can also be applied to the invention of (2), and it goes without saying. (3) Manufacturing method of grain-oriented electrical steel sheet with forsterite film The present invention is a method of manufacturing grain-oriented electrical steel sheet, which includes: containing C: 0.08mass% or less, Si: 2.0 ~ 8.0mass%, Mn : 0.005 ~ l.Omass% flat steel made of steel (also including thin flat metal. The same applies below) a step of rolling to a final plate thickness to make a steel plate; a step of applying recrystallization annealing to the above steel plate; The first buckle b annealing step applied to the steel sheet by the annealing method described in (1); Here, if the above-mentioned annealing release agent applied before annealing in the first batch annealing step is referred to as a first annealing release agent , The recrystallization annealing is performed before the application of the first annealing release agent, or after the application of the first annealing release agent and before the batch annealing, and each of the first annealing release agent is set The coating amount on one side is 0.005 ~ 5g / ιτί, 13 312XP / Invention Specification (Supplement) / 94-03 / 93137129 200525042 and has the step of applying continuous annealing to the above steel plate afterwards, and the second step containing MgO Annealing separator Cloth on the steel sheet, then applying a batch anneal step of the second batch annealing. The magnetic properties of this grain-oriented electromagnetic steel sheet and the coating properties of the magnesite coating are excellent. (4) Manufacturing method of grain-oriented electrical steel sheet without forsterite film The present invention is a method of manufacturing grain-oriented electrical steel sheet, which includes: containing C: 0.08 in ass% or less, Si: 2.0 ~ 8.0mass%, Μη: 0. 0 05 ~ 1.0 mass% of a flat billet made of molten steel rolled to a final sheet thickness to make a steel sheet; a step of applying recrystallization annealing to the above steel sheet; and the above steel sheet with (1 The annealing method described in the above) applies a batch annealing step followed by a process annealing step. Here, the recrystallization annealing is performed before the application of the annealing separating agent in the post-processing annealing step described above, or described in (1). After the annealing release agent is applied, it is performed before the batch annealing, and the coating amount per one side of the annealing release agent is set to 0. 0 5 to 5 g / ιτί. This grain oriented electromagnetic steel sheet has excellent magnetic properties and workability. Any of the inventions (3) and (4) above can be applied to a grain-oriented electrical steel sheet without using an inhibitor-forming component. In this case, the flat embryo is preferably a flat embryo made of molten steel having a composition that reduces the content of A 1 to 150 ppm or less and each of the contents of N, S, and Se to 50 ppm or less. . Further, in any of the above inventions (3) and (4), it is preferable that the step of rolling the flat slab to a final sheet thickness to form a steel sheet includes: applying hot rolling to the flat slab to form a heat The step of rolling a steel sheet; if necessary, the step of annealing a hot-rolled steel sheet to anneal the above-mentioned hot-rolled 14 312XP / Invention Specification (Supplement) / 94-03 / 93137129 200525042; An annealing step of cold rolling more than 2 times to form the final sheet thickness. (4) A more suitable form of the invention is a method for manufacturing a grain-oriented electrical steel sheet, which comprises: C: 0.08mass% or less, Si: 2.0 ~ 8.0 mass%, Mn: 0.005 ~ l.Omass% The flat embryo made of steel is subjected to hot rolling; secondly, cold rolling is applied once, or cold rolling is performed twice or more with intermediate annealing to obtain the final sheet thickness; followed by recrystallization annealing Step; and followed by the step of post-processing annealing performed by the annealing method described in (1); and setting the coating amount of the annealing release agent applied before annealing in the above-mentioned post-processing annealing to per side 〇. 〇 0 5 to 5 g / m2, or a method for manufacturing a grain-oriented electrical steel sheet, comprising: C: 0 · 08 mass% or less, Si: 2. 0 to 8. 0 in ass%, Μη: 0 , 005 to 1. 0 mass%, and at the same time, a step of applying hot rolling to a flat billet made of Hyun steel having a composition of reducing A1 content to 150 ppm or less and each of N, S, Se content to 50 ppm or less ; Secondly, apply cold rolling once, or cold rolling more than two times with intermediate annealing to make the most A step of plate thickness; a step of performing recrystallization annealing; and a step of performing post-processing annealing by using the annealing method described in (1); and setting an annealing separator applied before annealing in the above-mentioned post-processing annealing The coating amount is 0.05 to 5 g / m2 per one side. In this more suitable form of the invention, it is preferable that the annealing separator is composed of A 1 compound and S i compound as main components, and the ratio of A 1 compound to S i compound is converted to A 1 2 0 3 8 A 1 2 0 3 + S i 0 2) The value is 40 ~ 9 5 mass%, the viscosity is 25 in P a · s or less, and it is solution or colloid soluble 15 312XP / Invention Specification (Supplement) / 94-03 / 93137129 200525042 Liquid state. [Embodiment] The inventors of the present case have repeatedly studied the annealing release agent with excellent coating properties and adhesion after coating. It is found that firstly, the A 1 compound and the compound stable at high temperature are used as the main component, and at least By making the A 1 compound in a solution state or a colloidal solution state, the above problems can be solved. In addition, the inventors of the present case also found the appropriate viscosity of the above-mentioned annealing separator, the solid content ratio of the A 1 compound, and the appropriate coating amount when applied to a steel sheet. In the following, it will be explained based on the successful experiments of the invention. < Experiment 1> Manufactured by a continuous casting method from C: 0.020mass%, Si: 3.30mass%, Mn: 0.070mass%, and Sb: 400massppm and has been suppressed to A 1 * 38massppm, N: 33massppni, S: 18ppm, Se: Flat steel slab composed of components less than 10 ppm (under analysis limit). Then, the flat steel slab is subjected to cold rolling σ 1 time or cold rolling 2 or more times with intermediate annealing to form the final sheet thickness. Next, recrystallization annealing and post-processing annealing are applied to the cold-rolled steel sheet. Here, before post-processing annealing, an aqueous colloidal solution (solid concentration 3.0 mass%) of silica dioxide sol (colloidal silica) was used as an annealing separator, and each surface of the steel plate (both sides) was treated on one side. A range of from 0.1 to 3.0 g / πί was applied using a roll coater. After coating, the steel sheet is subjected to a baking treatment at a temperature of 250 ° C, and then allowed to cool. The amount of annealed release agent was determined from the difference between the weights of the steel sheets before coating and the calcination treatment, and this was used as the amount of the annealed release agent. 16 312XP / Invention Manual (Supplement) / 94-03 / 9313 7129 200525042 During post-processing annealing, it is held in a nitrogen atmosphere at 8 50 ° C for 30 hours, and then under argon at 100 ° C. Keep in air environment for 5 hours. For the obtained steel sheet, tests were performed on three items, such as the coatability of the annealing separator, the adhesiveness of the annealing separator after drying, and the annealing separation effect during post-processing annealing. The details of each performance evaluation method are described below. The evaluation methods of Experiments 2 and 3 and Examples described later are also the same. _Coatability The steel sheet after the annealing separator was applied was evaluated visually. 〇: Uniform coating on the entire steel sheet △: Coating on the entire steel sheet, but unevenness X: There are applied and uncoated places Brushing, while washing with running water for 10 seconds at a flow rate of about 1.0 m / s. Then, the water was removed with a squeeze rod (r i n g e r r ο 1 1), and the drying was performed under the condition of 2 0 0 ° C x 1 0 s. Then, the weight of the steel sheet was measured again, and the amount of the annealed release agent was calculated again. Then, the difference in the amount of the annealed release agent adhered before and after water washing was determined, and this was taken as the peeling amount. Based on the obtained peeling amount, it evaluated as follows. 〇: The peeling amount of the separating agent is 10% or less of the coating amount △: The peeling amount of the separating agent exceeds 10% of the coating amount and less than 80% X: The peeling amount of the separating agent is 80% of the coating amount % Or more • Annealing separation effect Apply a separating agent and apply 17 312XP / Invention Specification (Supplement) / 94-03 / 93137129 200525042 while applying a press load of 0.74 MPa for post-processing annealing. Then, the steel plate subjected to dazzling was peeled using a tensile tester, and the strength (peel strength) required for peeling was measured, thereby evaluating in the following manner. 〇: Fuse without steel plate (peel strength below 10 N) △: Fuse of steel plate was found in some cases (peel strength exceeds 10 N and less than 60 N) X: complete fusion of steel plate (peel strength 60 N or more) The test results are shown in Table 1. The annealing release agent used in Experiment 1 was good in terms of coatability and annealing separation effect, but under all conditions, the release agent had insufficient adhesion to the steel plate. Table 1 Coating amount (g / m) Viscosity (mPa · s) Coating release agent Adhesive peeling amount (g / m) Annealing separation effect Peel strength (N) 0.1 1 3. 1 〇Δ 0. 05 〇3 0 · 5 3. 1 〇Δ 0.20 〇0 1 3 · 1 〇Δ 0. 65 〇0 2 3. 1 〇X 1. 70 〇3 3. 1 〇X 2. 90 〇2 From the above experiment 1 It can be seen that, although the silica dioxide sol has an annealing separation effect during post-processing annealing, it has problems in the adhesion to the steel sheet as an annealing separator. Therefore, the inventors of the present application used silica sol as an annealing separator, and in order to improve the adhesion to the steel sheet, the effectiveness of adding alumina sol as a film-forming component was reviewed. < Experiment 2 > In the same manufacturing steps as Experiment 1, the surface of the steel plate (both sides) before post-processing annealing will be water-based with alumina sol (colloid alumina) and silica sol as the main components. Colloidal solution of annealing separator (solid content of 2.0 ni ass%) at a coating amount of 0.5 g / πί per side using a roller coater 18 312XP / Invention Specification (Supplement) / 94-03 / 93137129 200525042 coated. Next, the steel sheet is baked at a temperature of 250 ° C and allowed to cool. Then, as in Experiment 1, after being held in a nitrogen atmosphere at 850 ° C for 30 hours, it was subjected to processing annealing after being kept in an argon atmosphere at 1000 t for 5 hours. For the obtained steel sheet, investigations were conducted on the three items of coating properties of the annealing separator, adhesion of the annealed release agent after drying, and annealing separation effect during post-processing annealing in the same manner as in Experiment 1. Change the ratio of alumina sol to silica sol within the range of A 1 2 0 3 / (A 1 2 0 3 + S i 0 2) to 2 0 ~ 1 0 0 mass%, and make the annealing separate The viscosity of the agent varies within a range of 3.5 to 100 m P a · s. In addition, the viscosity of the annealed release agent was changed using alumina sols of different viscosities. The viscosity of the oxidized sol can be controlled by, for example, the shape of the sol particles or the solid content concentration. For example, feathers outside the sol particles are high-viscosity and low-viscosity when close to spherical (or granular) or ellipsoidal (or rod-like). Table 2 shows the experimental results when the ratio of the alumina sol to the silica sol was changed. When the ratio of the alumina sol is low, the adhesiveness of the annealing separator is insufficient. In addition, if the ratio of the alumina sol is too large, the film-forming effect becomes too strong, and it is difficult to achieve uniform coating on the steel sheet, resulting in poor appearance of the product. In addition, the annealing separation effect gave good results under all conditions. In addition, Table 3 shows the experimental results of changing the viscosity of the annealing separator. If the viscosity becomes higher, the coating property to the steel sheet will be significantly deteriorated, and a coated part and an uncoated part will occur. Since the uncoated part is subject to fusing of the steel sheet, in order to ensure good coatability and have an annealing separation effect, it is necessary to control the fact that the viscosity is 19 312XP / Invention Specification (Supplement) / 94-03 / 93] 37129 200525042 be confirmed. Table 2

Alumina sol / silica dioxide sol ratio Al2〇3 / (Al2〇3 + Si〇2) · mass% viscosity (mPa · s)-60 ~ 3.5 60 '~ 10 60 ~ Γ 25 60 ~ 50 60' Bu 100 < Experiment 3> Coating 〇_ Separation agent adhesion π ~~ Peeling amount Sg / ni) Annealing separation effect peeling IF " Degree (N) 〇〇U 0 0 〇ο 0 0 0 in —〇0 ~ ~ 0 Δ Δ r 丄 VJ _ ^ 28 45 Secondly, in the same manufacturing steps as in Experiment 1, for the surface of the steel plate (both sides) before post-processing annealing, alumina sol and silica will be the main ingredients The annealed separating agent (solid content concentration 2.5 mass%) composed of an aqueous colloidal solution was applied by a roller coater under each condition in a range of 0.001 to 6 g / rri per side as a coating amount. The viscosity of the annealed separating agent was set to 2 · 5 m Pa · s, and the ratio of the alumina sol to the silica sol was 75 mass% in terms of Al2O3 / (Al2O3 + Si02) conversion. Next, 'the baking is performed under the condition that the steel sheet reaches a temperature of 250 ° C, and the steel sheet is allowed to cool. Then, the same as Experiment 1 was performed in a nitrogen atmosphere at 850 ° C for 30 hours, and then annealed in a argon atmosphere at 1000 ° C for 5 hours. The obtained steel sheet was evaluated by the same method as in Experiment 1, regarding the coatability of the annealing separator, the adhesion of the dried separator after drying, and post-processing withdrawal 312XP / Invention Specification (Supplement) / 94-03 / 93137129 20 200525042 Investigation of 3 items of annealing and separation effect in fire. Table 4 shows the experimental results when the coating amount was changed. When the coating amount is very small, the effect of annealing separation is insufficient, and fusion of the steel sheet occurs. In addition, if the coating amount is increased, the adhesiveness of the annealing separator to the steel sheet is reduced. Based on the above, in order to ensure good adhesion to the steel sheet and have the effect of annealing separation, it is desirable to control the amount of the annealing separator applied. Table alumina sol / silica dioxide sol ratio Al2O3 / (Al2O3 + Si0): mass% viscosity (mPa · s) coating amount (g / m) coating release agent adhesive peeling amount (g / m) Annealing separation effect Peeling | strength d · 75 2.5 0.001 〇〇0 X 100 75 2.5 0.005 〇〇0] 〇10 75 2.5 0.05 〇〇0 〇0 75 2.5 0.5. 5 〇〇〇〇75 2. 5 1 0 0 0 0 0 0 0 0 75 2.5 2 0 0 0 0 0 0 0 75 2.5 3 3 0 0 0 0 0 0 75 2. 5 6 0 0 1. 2 0 0 From the above experimental results, it was newly discovered that as an annealing separator, Adopted as two

Compounds with excellent stability during high-temperature annealing such as silicon oxide, and A 1 compounds in solution or colloidal solution states are used as the main component, and the solid content ratio and viscosity of the A 1 compound are specified to obtain excellent coating properties and coating The close adhesion is then completed, and the present invention has been completed. Next, the annealing separator of the present invention, the method for annealing the grain-oriented electrical steel sheet, and the method for manufacturing the grain-oriented electrical steel sheet will be described in detail. First, the reasons for limiting the annealing separator will be described. The limitation is a general rule when applied to a steel sheet. As the main component of the annealing separating agent, the A 1 compound in a solution state or a colloidal solution state and a compound stable at high temperature, that is, having excellent stability at high temperature and not reacting or difficult to react during batch annealing 21 312XP / Invention Specification (Supplement) / 94-03 / 93137129 200525042 One or two or more compounds other than MgO which are well known. In addition, the compound which is stable at the above-mentioned high temperature may form a solution state or a colloidal solution state together with the A 1 compound. That is, the annealing separator may be in the form of a solution or a colloidal solution. Here, the state of being in a solution means a state in which the compound is dissolved in a medium such as water or an organic solvent. The state of the colloidal solution refers to a state in which particles of the compound of about 100 m or less are stably dispersed in the medium through a structural portion such as a functional group having affinity for the medium. In any case, the liquid that becomes the medium is collectively referred to as a solvent. The colloidal solution is transparent in appearance without suspension, so it is similar to the solution, but the presence of colloidal particles can be confirmed by light scattering measurement. The main component refers to a component other than an auxiliary agent or an additive described later. Therefore, the proportion of the main component in the whole of the annealed separating agent component (that is, the object forming a solute or a colloid) after drying is about 65 m a s s% or more, and more preferably 75 m a s s% or more. The liquid used as the solvent is not particularly limited, and either water or an organic solvent can be used. As the organic solvent, methanol, isopropyl alcohol, ethylene glycol, or the like is generally used, but it is not limited thereto. From the standpoint of cost or the diversity of the selection of the compounds, water is preferred as the solvent. In this case, an organic solvent of about 50 in a s s% or less may be mixed with water for the purpose of adjusting liquid characteristics and the like. The above-mentioned case where water is the main solvent is called an aqueous annealing separator. The A 1 compound and the above-mentioned stable compound at high temperature hardly react with red aluminum and iron like the conventional MgO used in the annealing separator, 312XP / Invention Specification (Supplement) / 94-03 / 93137129 22 200525042 As a result, a film that significantly deteriorates punchability like a forsterite film is formed. Therefore, it is very effective when supplying a grain-oriented electrical steel sheet excellent in punchability. The main component of the annealing separator is to use two or more compounds in order to obtain a high degree of annealing separation effect by using a stable compound at high temperature, and use a solution-like or colloidal A 1 compound to obtain a good film-forming effect. The combination of the two effects can effectively act as an annealing separator for steel plates with excellent coating properties and adhesion of the steel plate after coating, and especially meets the requirements for the annealing separator for grain oriented electromagnetic steel plates. characteristic. The A 1 compound is limited to a compound that forms a colloid in a solvent such as water in order to ensure the film forming function. That is, if the A 1 compound is not in a colloidal state, the film-forming effect cannot be exhibited, and adhesion cannot be obtained. For example, in the case where alumina is applied as a slurry or suspension, no film is formed. The particle diameter of the colloid of the A 1 compound is preferably set to about 50 nm or less. As for the lower limit, there is no suitable particle size limit, and the effect can be fully exerted even near the analysis limit. In the case of an aqueous annealing separator, it is preferable that the A 1 compound is an aluminum compound having a via group and an organic acid group and / or a dehydration reaction product (partial dehydration is also possible. The same applies hereinafter). Further preferred are aluminum compounds and / or dehydration reactants thereof composed of A1, a hydroxyl group, and an organic acid group. Specific examples include acetic acid, acetic acid, acetic acid, acetic acid, acetic acid, oxalic acid, acetic acid, lactic acid, and citric acid. One compound of the acid, or a mixture of two or more of these compounds. Among them, basic aluminum acetate is preferably represented by the molecular formula A 1 X (0 H) y (C Η 3 C 0 0) y (χ, y, and ζ are 1 or more), and Al2 (OH) 5 ( CH3COO) 23 3] 2XP / Invention Specification (Supplement) / 94-03 / 93137129 200525042 is particularly suitable. It can exist from a molecular-level dissolved state to a colloidal state of about several nm, and can be suitably used as a coating liquid raw material. It is known from thermal analysis that there is a large dehydration reaction peak at about 200 ~ 230 ° C. After heating, an intermolecular network structure formed by dehydration condensation is formed to form a film. A part or all of the above-mentioned basic aluminum acetate and the like may be subjected to a dehydration reaction. In the case where an organic solvent is used as a solvent, as a suitable A 1 compound, the same thing as in the case of an aqueous annealing separator can be applied. Known compounds that are stable at high temperatures other than MgO can be used and are not particularly limited, but examples thereof include Si compounds, Sr compounds, Ca compounds, Zr compounds, Ti compounds, and Ba compounds. Specific compounds include oxides such as Si02, SrO, Ti02, BaO, and CaO. In addition, in order to contain the above-mentioned stable compound at a high temperature in a solution or a colloidal solution, for example, in the case of an aqueous annealing separator, it is preferable to use a chemically changed form having a hydrophilic group such as a hydroxyl group. However, in the case of a compound which is stable at a high temperature, as another method, it may be designed to form a state in which a surface is coated with a known hydrophilic substance in a solvent. When an organic solvent is used as a solvent, a lipophilic group is also used, and it can be designed by the same technical idea. In addition, the high temperature when the compound is stable under high temperature refers to the annealing temperature, but in the case of the use of the grain oriented steel sheet, it is sufficient to stabilize at 1 200 ° C, and more preferably 1 300 Stable at ° C. At this temperature, the compound itself does not substantially react with the steel plate or oxides on the surface of the steel plate (S i 0 2, FeO, Fe304, Fe2Si04, etc.). The above compounds can be improved by coexistence with the A 1 compound. 24 3 12XP / Invention Specification (Supplement) / 94-03 / 93137129 200525042 The coating effect of the fire separating agent, including coating properties and annealing From the standpoint of separation performance and the like, Si compounds are particularly suitable. As the Si compound, colloidal silicon dioxide, so-called colloidal silicon dioxide (c ο 1 1 o i d a 1 s i 1 i c a), is particularly suitable because of its high stability and low cost with oxidized ig sol. Colloidal dioxide is an inorganic colloid with S i 0 2 as its main component, which is often amorphous. In addition, A1 compounds such as alumina particles that are not part of a solution / colloid solution (referred to as non-colloidal system A1 compounds) are stable at high temperatures, but their coating properties for solution / colloid solution A1 compounds The improvement effect is low. Therefore, although the addition of the non-gum system A 1 compound as a part of the main component itself is not prohibited, it is preferable to contain a compound which is stable at a high temperature other than the non-gum system A 1 compound. The non-gum system A 1 compound is not considered in the calculation of the solid content ratio described later. When the solid content ratio of the compound A 1 is in accordance with the solid content ratio represented by the following formula (1), it is preferably 40 to 95 mass%. Solid content ratio of A 1 compound = (solid content of A 1 compound) / {(solid content of A 1 compound) + (solid content of compound stable at high temperature (and)) 丨 ... Formula (1) where A 1 The solid content of the compound is converted into A 1 2 0 3, and the stable compound at the above high temperature is converted into the main compound after firing. For example, if it is a silica dioxide sol, it is based on silicon dioxide, that is, Si02, and if it is a titanium dioxide sol, it is based on titanium dioxide, i.e., Ti02. In addition, even in the case where a roasting step is not specifically set, it is converted into a main compound generated when the roasting is performed. 25 312XP / Invention Specification (Supplement) / 94-03 / 93137] 29 200525042 In the case where the solid content is substantially composed only of these compounds, formula (1) is replaced by formula (3). The solid content ratio of the A 1 compound = (solid content of the A 1 compound) / (full solid content) ... Formula (3) Here, the solid content refers to the content of the annealing separator component after drying. If the solid content ratio of the A 1 compound is 40 hi a s s% or less, the A 1 compound, which is a film forming component, is insufficient, resulting in insufficient adhesion of the annealing separator. In addition, when the solid content ratio exceeds 95 m a s s%, the amount of the highly reactive A 1 compound is too large, and the coating liquid is unstable. Therefore, a uniform film cannot be formed, resulting in a poor appearance of the product. The solid content ratio of the A 1 compound is preferably 50 m s s%, more preferably 60 mass%, and more preferably 70 mass% or more. As a stable compound at high temperature, when using at least one compound selected from the group consisting of Si compound, Sr compound, Ca compound, Zr compound, Ti compound, and Ba compound, the solid content of A1 compound The ratio is replaced by the following formula (2). Solid content ratio of A 1 compound = (solid content of A 1 compound) / {(solid content of A 1 compound) + (solid content (and) of at least one of the above compounds) 丨 ... Formula (2) The solid content is preferably the value converted to the weight of each of the following compounds: A1 compound ... AhCb; Si compound- " SiC ^; S r 4 compound ... S r 0; C a 4 compound C a 0; Z r compounds ... Z r (h; Ti compounds ... Ti 〇 2; B a compounds ... B a 0. 26 312XP / Invention Specification (Supplement) / 94- 03/93137129 200525042 When the stable compound at high temperature uses Si compound, that is, when the solid content is mainly composed of A 1 compound and Si compound, it is best to convert the ratio of A 1 compound to S 1 compound into A 1 The value of 2 0 38 A 1 2 0 3 + S i 0 2) is set to 40 to 95 mass%. The viscosity of the annealed release agent is specified to be 25 (m P a · s) or less. If the viscosity exceeds 25 (m P a · s), the coatability is significantly deteriorated, preventing uniform application of the annealing release agent on the steel sheet. As a result, uncoated portions were generated, which caused the steel plates to adhere to each other during post-processing annealing. In addition, the viscosity in the present invention is a value obtained by measuring the viscosity of the annealed separating agent at a liquid temperature of 25 ° C using an Oschwa (0 s t w a 1 d) viscometer. In addition, even when a colloidal slurry is used instead of a colloidal solution, the uniformity of coating cannot be obtained. It can be inferred that the viscosity is not suitable and the viscosity change caused by the agglomeration of colloids in the slurry is a major factor. In addition, by adding S (simple substance) or an S-containing compound (hereinafter collectively referred to as an S-containing compound) to the annealing separator, it is possible to impart good magnetic properties to the grain-oriented electrical steel sheet. Although the reason for this is not clear, it is speculated that during batch annealing, the S-containing compound is decomposed, so that S penetrates into the steel and segregates at the grain boundaries. That is, since the growth of the particles is suppressed by the segregated S, the stabilization of the secondary recrystallization is caused. In addition, if the amount of segregated S is too large, it may cause secondary recrystallization defects. In the case of avoiding such a situation, it is preferable that the solid content ratio of the amount of the S-containing compound to the annealing separator component after firing is set to about 25 m a s s% or less. In addition, even in the case where the baking step is not specifically set, the solid content ratio of the S-containing compound 312XP / Invention Specification (Supplement) / 94-03 / 93137129 27 200525042 generated during the baking is evaluated. The S-containing compound is not particularly limited, but inorganic S compounds such as sulfates (including sulfites and the like) and metal sulfides are preferred. Specific examples include europium sulfate, magnesium sulfate, and magnesium sulfide. As the method for applying the annealing separator, various methods such as a roll coating method, a flow coating method, a spray method, and a knife coating method which are generally used in the industry can be applied. In addition, it is preferable that the annealing separating agent of the present invention can be heated after coating to perform a baking treatment. As for the firing method, methods such as a hot air method, an infrared method, and an induction heating method that are generally implemented are applied. The firing conditions may be set in accordance with various conditions, but generally a suitable temperature is about 150 to 400 ° C, and a suitable time is about 1 to 300 seconds. In addition, in order to further improve the coating property of the annealed release agent or the adhesion property to the steel sheet, additives such as a surfactant, a preventive agent, and a recording agent may be blended. Regarding the content of the additives, in order to maintain a sufficient annealing separation effect as an annealing separator, it is desirable to set the content of the annealing separator after drying to about 10% or less. In addition, as the surfactant, any of commercially available nonionic, anionic, and cationic systems can be used. Similar to the surfactant, the rust preventive is not limited in type, and it can be used commercially. Although the annealing and separating agent of the present invention is particularly suitable for the application to the directional electromagnetic steel sheet, the application to other steel sheets is not prohibited. In addition, although the annealing separator of the present invention is particularly effective when the steel strip is directly wound into a coil and heated in a furnace, it can also be applied to steel plate 28 312XP / Invention Specification (Supplement) / 94-03 / 93137129 200525042 Cases of overlapping heat treatment. Next, the conditions suitable for the manufacture of the grain-oriented electrical steel sheet according to the present invention will be described below. Regarding the component composition of the finished plate and the starting material (fused steel or flat steel blank), any one of the components known to be suitable for the grain-oriented electrical steel sheet can be applied. Hereinafter, the reasons for limitation of each component will be described with respect to a suitable molten steel component in a representative component system. C: 0 · 0 8 mass% or less If the C content exceeds 0.08 mass%, it is difficult to achieve a reduction of C to less than 50 in assppm without magnetic aging. Therefore, it is best to Set to 0. 0 8 ni ass% or less. In particular, the lower limit does not need to be set, but in the industry, about 5 m assppm is the lower limit.

Si: 2.0 ~ 8.0 mass%

Si is an effective element for improving the electrical resistance and iron loss of steel. In order to obtain the effect, Si should be contained at least 2. Omass%. On the other hand, if it exceeds 8. 0 mass%, the workability or magnetic flux density will decrease. , So it's best to set the upper limit to 8.0mass%. Therefore, the preferred Si content is 2.0 to 8.0 mass%. Mn: 0.005 to 1.0 ni ass% Mn is an element effective in improving the hot workability, and it is preferable to add more than 0.05 m a s s%. On the other hand, excessive M η will decrease the magnetic flux density of the finished plate. From this viewpoint, the preferable Mη content is 1.0 mass% or less. Therefore, the preferred Mη content is 0.005 ~ l.Omass%. In the manufacture of directional electromagnetic steel sheets, in order to develop the Gaussian orientation during secondary recrystallization, an element for forming an inhibitor is generally added (inhibitor formation 29 312XP / Invention Specification (Supplement) / 94-03 / 93137129 200525042 ingredient). However, the fact that the Gaussian orientation is developed by reducing the impurity elements of the steel has recently been used to reduce the A 1 content to 15 0 in ass in order to use the secondary relocation grains without using inhibitors. Se content was reduced to below 50 massppni. From the viewpoint of such characteristics, it is more preferable, for example, it is further preferable; 100 m a s s p p m or less. However, the reduction of such ingredients increases, so that the remaining within the above range will not be the status quo, and the lower limit of the content is limited to lOniassppni in order to reduce the cost. In addition, when an inhibitor is used, these elements are added instead. For example, in the case of using A in general, Timing mouth A 1 ·· (K 0 1 5 ~ 0. 0 4 mass% and N:%, in the case of using BN as an inhibitor, add B% and N: 0.005 ~ 0.015 mass%, in the case of using a Mi inhibitor, any of the addition forces σ S e and S is 0. In addition, adding S b and / or S η to a total of 0 · 0 0 5 to 0 can further improve the direction of the electromagnetic steel sheet. Improved magnetic properties. In addition, even if each contains 0.1 mass% or less and 0.2111833% or less each ?? (: 11, (: 1 ~, with Ni, there is no problem. Also, residual From the dazzling steel with the above composition, ordinary size flat embryos can be produced by ordinary manufacturing methods, or straight 312XP / Invention Specification (Supplement) / 94-03 / 93137129 can also be used without suppression. Crystallize to get Gaussian ppm or less, make N, S, and fractions as low as possible. Set the A 1 content in the magnetic L to sometimes cause any problems in cost. According to this, each element is about the suppression applied according to the application. Agent 1 N as an inhibitor 0. 005 ~ 0 · 015 mass ·· 0 · 001 ~ 0 · 006mass iSe and / or MnS as • 005 ~ 0 · 06mass% 〇 • 1 mass%, it is better to add force. Ge, Mo, Te, B i 5 0.5 mass% or less containing iron and unavoidable block making method or continuous continuous casting It is also possible to manufacture thin cast slabs (so-called thin flat slabs) with a thickness of 30 200525042 degrees or less than 100 mm. Flat slabs are reheated and hot rolled by the usual method, but they are directly heated without being heated after casting. Yes. In the case of thin slabs, hot rolling can be performed, or hot rolling can be omitted, and the process can be directly performed. The hot-rolled steel sheet can be annealed (hot-rolled steel sheet annealing) as required. Especially in In the case where a band-like structure is formed during hot rolling, in order to achieve the primary recrystallized structure of the whole grain to promote the development of secondary recrystallization, it is preferable to perform annealing on the hot-rolled steel sheet. The annealing temperature of the steel sheet is set to more than 800 ° C. On the other hand, if the grain size is excessively coarsened due to the annealing of the hot-rolled steel sheet, it is not suitable for the realization of the primary recrystallization structure of the whole grain, so it is best to Setting of annealing temperature for hot rolled steel sheet 1 1 0 ° C or less. Therefore, in order to highly develop the Gaussian structure in the finished sheet, the annealing temperature of the hot-rolled steel sheet is preferably set to 8 0 ° C or higher and 1 1 0 0 ° C. In addition, hot rolling A suitable annealing time for steel sheet annealing is 1 to 300 seconds. Second, cold rolling is performed more than once to make a cold rolled steel sheet, and then recrystallization annealing is performed. When cold rolling is performed twice or more, intermediate annealing is interposed between the cold rollings. The intermediate annealing is preferably performed at a temperature of 900 to 12 ° C for a time of about 1 to 300 seconds. In addition, in order to further develop the Gaussian structure, the temperature of cold rolling may be increased to 100 ~ 250 ° C. This type of cold rolling is sometimes referred to as warm-rolling-but it is considered a type of cold rolling in this case. For the same purpose, the aging treatment may be performed once or more than 100 ° C to 250 ° C during cold rolling. 31 3 12XP / Invention Specification (Supplement) / 94-03 / 93137129 200525042 Recrystallization annealing is best performed by continuous annealing for the purpose of forming a primary recrystallized structure. If decarburization is required for recrystallization annealing, set the environment to a humid environment, and if decarburization is not required, perform it in a dry environment. The preferred recrystallization annealing conditions are about 1 to 300 seconds at 750 to 110 ° C. In addition, the amount of C contained in the steel sheet of the secondary recrystallization annealing (post-work annealing, or the first batch annealing when the post-processing annealing is divided into two batch annealings) is adjusted to 1 ◦ 0 ~ 2 5 0 Massppm is particularly suitable for increasing the magnetic flux density in a grain-oriented electrical steel sheet without an inhibitor. The amount of C may be adjusted by recrystallization annealing or by other methods. It is also possible to apply the technique of increasing the amount of Si by the silicon immersion method to, for example, a steel sheet after recrystallization annealing. The coating of the annealing separator of the present invention is performed before or after the recrystallization annealing. The conventional annealed release agent has poor adhesion to the steel sheet, and the application of the annealed release agent before recrystallization annealing is impossible from the viewpoint of contamination of the production line caused by peeling during recrystallization annealing. This also applies to the case where an annealing separator containing MgO as a main component is required to be heated for a long time in the formation of a film. However, the annealed release agent of the present invention has good adhesion to the steel sheet, and there is no need to worry about contamination of the production line caused by peeling, so it can be applied before or after recrystallization annealing. In this step, in order to exert the effect of preventing close adhesion to the steel sheet, it is preferable to set the coating amount of the annealing release agent of the present invention to not less than 0.5 g / ηΐ. On the other hand, in order to ensure the adhesiveness of the annealing separator, it is best to set the weight attached to 32 312XP / Invention Specification (Supplement) / 94-03 / 93] 37129 200525042 to 5 g / ιτί or less. Therefore, the application amount of the annealing release agent is set in the range of 0.005 to 5 g / iri. A further preferred lower limit is 0 · ηΐ, and a further preferred upper limit is 2 g / rrf. In addition, although the appropriate coating amount during the manufacture of the grain-oriented electrical steel sheet is as described above, it can be used outside the above-mentioned range according to the respective heat treatment conditions or required quality. The annealed release agent may be applied to only one side of the steel sheet, or may be applied to the steel sheet, but it is preferable to apply it to the surface from the standpoint of obtaining an effect. Although the composition of the annealed release agent on the surface of the steel plate is not prohibited, it is best to apply the same annealed release agent on both sides in the process of manufacturing without a forsterite film and having excellent magnetic properties and properties. In the case of a grain-oriented electrical steel sheet, after recrystallization annealing and application of the pyrophoric separating agent, batch annealing and post-process annealing are performed. The purpose of post-annealing is to carry out secondary recrystallization and reduce impurities). As the annealing conditions, it is possible to apply the well-known conditions for achieving this item. The annealing temperature after processing is about 7 50 ~ 130 0 ° C, but the first half is set at 7 50 ~ 100 0 ° C and the second half is about 9 0 0 to 1 3 0 ° C is also acceptable. Here, secondary recrystallization is mainly promoted in the part, and purification is mainly promoted in the second half. The subsequent processing annealing time is about 1 to 300 hours in terms of the holding time in the above temperature range. In addition, in the case of the conventional application of an annealing separator containing MgO as a main component, since a thicker film is formed, the time required for purification is longer than that in the case where no separating agent is applied. However, although the annealing agent of the present invention has film formation of the A 1 compound, it still has the effect of not hindering the purification. 3 12XP / Invention Specification (Supplement) / 94-03 / 93137129 It is best 05g / . Likou Gongming withdrawal processing (pure 0 is better than the first half of the best technical conditions phase separation view 33 200525042). In the case of post-annealing in the state containing C about 1 for the purpose of improving magnetic properties, it is preferred After that, C is reduced to 50 ppm without magnetic aging. The method includes a method of decarburization in post-processing annealing, and a method of adding a decarburization step later. To post-process annealing, especially in the second half, it contains hydrogen. High temperature annealing on the environment is sufficient. On the other hand, as additional to post-processing annealing, there are (1) annealing in an oxidizing environment (decarburization annealing), surface grinding to remove surface graphite, (3) by chemical Means electrolytic washing, chemical grinding, plasma irradiation, etc. In addition, the reason for decarburization is that the decarburization in the steel surface is completed before the post-processing annealing is completed, and the decarburization in the steel is completed. The phenomenon is the following mechanism. C forms a temporarily stable Xueming in the steel, and graphite is formed in an activated state with high energy. Therefore, before the precipitation of the Xueming carbon body in the red aluminum iron, the stone The state diagram of the pure iron can be inferred that the melting degree of graphite is slightly lower. Therefore, it can be inferred that the concentration of solid solution C on the surface is reduced, so the concentration formed by solid solution C on the surface layer is generated. The gradient is then made from red aluminum. However, if post-processing annealing is used, if 312XP / Invention Specification (Supplement) / 94-03 / 93137129 00 to 250niassppm is formed on the surface, it will be less than the end of the secondary recrystallization. C reduction And decarburization in the post-processing annealing fire, and the implementation of the decarburization step at 100 ° C within the post-processing is effective, (2) borrowing means (2) or (3) by mechanical means to remove surface graphite, and C using graphite The type can be presumed to be a carbon body, for example, on the surface, C is precipitated into the surface layer during cooling. Since the melting of the cuming carbon body is as small as that of graphite and iron in red aluminum iron, it will decarburize. Dense or firm coatings (such as those applied to conventional annealing and separation with M g 0 as the main component), surface activation is impeded, and as a result, graphite is also impeded in the surface layer of steel plates. However, the present invention The excellent adhesion of the annealed release agent, However, it is not uncommon for the precipitation of graphite on the surface of the steel sheet. Although the reason is unknown, the above-mentioned decarburization method can still be suitably used after the post-processing annealing, and the flattening annealing is added to the tension to reduce the iron loss. It is also possible to perform this annealing in a humid environment, thereby performing decarburization at the same time (one of the methods of (1) above. In addition, after the post-processing annealing, it is also possible to further apply the technology of immersion by silicon immersion. It is necessary to further reduce the effect of iron loss. In the case where multiple steel plates are laminated and used for iron cores, it is effective to improve the lamination loss by coating the surface edge of the steel plate after flattening annealing. Especially to ensure good punching It is preferable that the organic coating of the resin is used as the insulating coating. On the other hand, in heavy cases, it is preferable to use an inorganic film as the insulating film. In addition, there is no need to specifically set the step of removing the annealing separator only. In the case of manufacturing an electromagnetic steel sheet having excellent magnesium mullite film properties and magnetic properties, after the recrystallization annealing and the coating of this release annealing are performed, The performance of the second recrystallization, the first fire. As the annealing conditions at this time, a common condition for performing secondary recrystallization can be applied. The preferred conditions are about 750 to 110 ° C and about 1 to 300 hours. Then, the formation of magnesite in the second batch annealing is used as its preparation stage. Annealed internal oxygen 312χρ / Invention Specification (Supplement) / 94-03 / 93〗 37129 The precipitation film has a good shape (the shape is flat). In the case of Si, it is a body of iron. Orientation Separation agent Batch de-annealing 〇 Membrane, and formation of coating 35 200525042 (subscale). For the purpose of improving the magnetic characteristics, in the case where the first batch annealing is performed directly in a state containing C in a specified amount, it is preferable to also perform a simultaneous annealing when forming the continuous oxidation of this internal oxide film. carbon. The annealing conditions (time, temperature, environment, etc.) of the continuous annealing described above can be easily and stably formed in the subsequent batch annealing by using known annealing conditions. The preferred annealing temperature is about 750 ~ 100 ° C, the preferred annealing time is about 1 ~ 300 seconds, and the preferred environment is an oxidizing environment composed of hydrogen and nitrogen. Prior to the continuous annealing described above, it is not necessary to provide a step of removing the annealing separating agent of the present invention. That is, even if a forsterite film is added to the annealing separator of the present invention, the adhesion of the forsterite film is still good, and the presence of the annealing separator of the present invention does not hinder purification. Next, an annealing separator containing MgO as a main component was coated on the surface of the steel sheet, and a second batch annealing was performed. Since this second batch of annealing is performed under the objectives of formation of the magnesite stone film and purification of impurities, the well-known annealing conditions that can achieve these two purposes can be applied. A preferred annealing temperature is about 900 to 130 ° C, and a preferred annealing time is about 1 to 300 hours. In addition, an annealing separator containing M g 0 as a main component is known. For example, as the solid content, it is best to set M g 0 ·· about 8 0 ~ 9 9 in ass%, and set the residue as selected from T i 0 2, S r S Ch, M g S 0 4 and so on as required. More than one is more suitable for use. After the second batch annealing, it is also possible to further apply the technique of increasing the amount of Si by dipping silicon. Then, a tension film is applied and fired as necessary. In addition, 36 3] 2XP / Invention Specification (Supplement) / 94-03 / 93137129 200525042 The shape can be trimmed by a flattening annealing, and a flattening annealing that also serves as a tension film can be performed. The meaning of the directional electromagnetic steel sheet of the present invention is an electromagnetic steel sheet exhibiting secondary recrystallization. Therefore, not only the Gaussian orientation, but also the secondary recrystallization of the cube orientation ({1 0 0} < 0.01 > orientation or 丨 1 0 0 丨 < 0 1 1 > orientation) is also included in the scope of patent application for this case. Known methods can be applied to the accumulation of cube orientations. For example, the control can be performed by using the rolled aggregate structure, and the recrystallization step is the same as that in the case of secondary recrystallization in which the Gaussian orientation accumulation is expressed. [Examples] (Example 1) A grain-oriented electrical steel sheet having excellent magnesium mullite quality and magnetic properties was prepared according to the following method. Manufactured by the continuous method, containing C: 0.020mass%, Si: 3.35mass%, Mn: 0 · 0 0 0 0 0 0 0 0 0 0 0 0% and S b · 3 8 0 massppm, and the component for forming the formulation contains Al: 320 massppni and N: 80massppm, and the remainder is a flat steel blank composed of iron and unavoidable impurities. After heating the flat steel blank at 120 ° C, it was processed into a hot-rolled steel sheet having a thickness of 2.0 mm by hot rolling, and the hot-rolled steel sheet was annealed at 1050 ° C for 60 seconds. bell. Then, cold-rolled steel sheet with a thickness of 0.30 mm was subjected to recrystallization annealing in a dry environment at a dew point of 45 ° C at 90 ° C for 10 seconds. After the recrystallization annealing, the first batch annealing is performed. The annealing separator is applied before or after recrystallization annealing as shown in Table 5. The application of the annealing separator is performed by using a roll coater, and then the baking temperature of the steel plate is 37 312XP / Invention Specification (Supplement) / 94-03 / 93137129 200525042 (plate temperature) is 2 50 ° C, and Let it cool. The roasting is performed by propane gas direct firing. The first batch annealing was performed at 850 C in a nitrogen atmosphere for 40 hours to complete the second recrystallization. Then, investigate the coating properties of the annealing release agent, the adhesion of the annealing release agent after drying, and the annealing separation effect after the first batch annealing. For these samples with good characteristics, further steps are performed. Made into finished boards. In the subsequent steps, first, continuous annealing is performed to form a good internal oxide film, and then an annealing separator containing MgO as a main component is applied. Since the first batch annealing is performed in a state where C remains at 100 to 150 m a s s p p m, decarburization is also performed at the same time as continuous annealing for forming an internal oxide film. Continuous annealing is performed in an oxidizing environment with a dew point of 55 ° C, and at 85 ° C for 120 seconds. The annealing separator for the second batch annealing uses solids containing MgO: 95 丨 11 & 53% and 11 丨 02: 5111355%. Next, a second batch annealing was performed in a dry hydrogen environment at 12 ° C for 5 hours. Then, coating, baking and stress relaxation tempering of the tension film are performed at the end. Tensile coatings are those which contain phosphoric acid, chromic acid, and colloidal silica, and are fired at 800 ° C. Stress relaxation annealing is performed in a nitrogen environment at 800 ° C for 3 hours. Table 5 shows the components and application conditions of the annealing separator. The annealing and separating agent based on the powder of Si 0, A 1 2 0 3 as the main component is coated with an aqueous slurry except for N 0.26, and N 0 · 2 6 is 5 mass% in solid form. Formula 38 312XP / Invention Specification (Supplement) / 94-03 / 93137129 200525042 suspended in alcohol and spray-coated. For those other than powder, the dilution ratio varies depending on the coating amount, but all are diluted with water to form a colloidal solution and applied. Lithium sulfate, magnesium sulfate, and magnesium sulfide, which are added as auxiliary agents, are added at 3 w t% each. Solid contents other than those shown in Table 5 are not added, and surfactants (non-ionic), etc., which are 0.5 m a s s% or less, are appropriately added. For the annealing separating agent used in the first batch annealing, the order of the annealing separating agent coating step (different before or after recrystallization annealing), the coating property of the annealing separating agent, and the density of the annealing separating agent after drying. The conformability and the annealing separation effect after the first batch annealing are shown in Table 6. No. 14 and 19, because the viscosity of the annealed release agent is outside the scope of the present invention, the coatability is significantly poor, and the steel plates are closely adhered to each other in the parts that have not been applied. The ratio of the A1 compound to the Si compound in Nos. 12 and 15 is outside the appropriate range of the present invention. Since the amount of the A 1 compound in the film forming component is small, the adhesion of the annealing separator to the steel sheet is poor. On the other hand, No. 15 has a large amount of the highly reactive A 1 compound, and the coating solution is unstable, so that a uniform film cannot be formed. As a result, the appearance is poor. Since the main components of the annealing separator are outside the scope of the present invention, the adhesion to the steel sheet is insufficient. No. 5 Due to insufficient coating amount of the annealing release agent, the steel sheets were closely adhered to each other during post-processing annealing. Ν〇.17 Due to too much coating amount, it showed insufficient adhesion to the steel sheet, and peeling occurred. Ν ·· 3,4,6,7,12, and 26 are used to separate the application of the annealing separator into two procedures before and after recrystallization annealing. The annealing and separating agent of the present invention is independent of the coating order of the annealing and separating agent, and can obtain good coating properties of the annealing and separating agent, adhesion of the annealing and separating agent after drying, and the first 39 3] 2XP / Invention Specification ( Supplement) / 94-03 / 93】 37〗 29 200525042 Annealing separation effect after batch annealing. It was found in Comparative Examples Nos. 3, 4, and 26 that the annealing separation effect was different due to the application order of the annealing separation agent. The reason is presumably that in the case of coating before recrystallization annealing, these annealing release agents, which have poor adhesion to the steel sheet, will peel off during recrystallization annealing, causing the first batch annealing to adhere to the steel sheet. The annealing separation dose becomes smaller, so that the steel plates are closely adhered to each other. On the other hand, in the case where coating is performed after recrystallization annealing, the amount required to prevent the steel plates from adhering to each other remains on the steel plate due to the small amount of peeling. Therefore, the steel plates do not adhere to each other. When the subsequent steps are applied to a sample to which the annealed separating agent of the present invention is applied to prepare a finished board, the magnetic characteristics, forsterite film characteristics, and A 1, C, N, S after the second batch annealing And S e content (in red aluminum and iron, that is, the analysis result after removing the coating on the surface of the steel plate) is shown in Table 7. The characteristics of the forsterite film are that the sample after stress relaxation annealing is wound on a cylinder, and the evaluation is performed according to the minimum bending radius without film peeling. The magnetic properties were measured using an Epstein test piece of 3 × 3 0 0n, which was performed in accordance with J I S C 2 550. Bs is the magnetic flux density (T) of the magnetizing force 800A / ηι, and Wi7 / 5G is the iron loss value (W / k g) at a frequency of 50 Hz and a maximum magnetic flux density of 1 · 7 T. In the case where the annealing separator of the present invention is applied, the magnetic properties and the properties of the forsterite film are both achieved, and impurities are purified without any problems. In addition, when S-containing compounds were added as auxiliary agents (No. 0.8, 10, and 1 1), further improvement in magnetic characteristics was found. 40 312XP / Invention Specification (Supplement) / 94-03 / 9313 7129 200525042 Table 5

No. Coating amount of the main component of the separating agent (g / m0 viscosity (niPa · s) oxygen · (; flap) · dioxygen (solvent) ratio Al2〇 / (Al2〇3 + Si〇2): mss% Remarks A1 chemical & 4 do not Si chemical correction other 1 A1 association end--1.2-100 bb | Intersection 2-Si〇2 powder-1.2-0 Intersection 3 Α1'Λ 粉 sia powder-1.2-60 Intersection 4 — Colloidal Dioxin — 1.2 2.5 0 tbl Interaction Example 5 Alkali 丨 Hydroxyacetate A1 Colloidal Dioxin (^ — — 0.001 1.8 75 Interaction Example 6 Alkaline Acetic Acid A1 Colloidal Dioxin_ — 0.05 1.8 75 Invention Example 7 Base 1 ± Acetic Acid A1 Colloidal Dioxin Diol—0.1 1.8 75 Invention Example 8 Alkaline Acetic Acid A1 Colloidal Dioxonite Jil Acid Sr 0.1 1.8 75 Invention Example 9 Assay Acetic Acid A1 Colloidal Dioxin w — 0.5 1.8 75 Invention Example 10 Acetylic Acetic Acid A1 Colloidal Dioxa Sulfate Mg 0.5 1.9 75 Invention Example 11 Acetylic Acetic Acid A1 Colloidal Dioxa Sulfate Mg 0.5 1.7 75 Invention Example 12 Test 1 * Raw Acetic Acid A1 Colloidal Dioxin — 1.2 3.2 25 Invention Example 13 Base 1 ± Acetic Acid A1 Colloidal Dioxin Cry — 1.2 1.8 75 Invention Example 14 Base 11 Acetic Acid A1 Colloidal Dioxin — 1.2 50 75 cross 15 Alkaline acetic acid A1 — — 1.2 2.5 100 Example of cross-linking 16 Alkaline acetic acid A1 colloidal dioxin β — 3 1.8 75 Invention example 17 Alkaline acetic acid A1 colloidal dioxin — — 6 1.8 75 Example 18 Alkali 11 A1 colloidal dioxin hydrochloride — — 1.2 1.9 75 Invention Example 19 Alkali 14 A1 colloidal dioxin hydrochloride — 1.2 100 75 Example 20 A nitric acid A1 colloidal dioxin — 1.2 3.5 75 Examples of invention 21 Glycolic acid A1 colloidal dioxin tender — 1.2 2.1 75 Invention Example 22 Alkali ft Lactic acid A1 Colloidal dioxin toxyl — 1.2 2.5 75 Invention example 23 Alkali rigid A1 colloidal dioxin — 1.2 2.4 75 Invention Example 24 Alkali oxalic acid A1 colloidal dioxin — 1.2 3.1 75 Invention Example 25 Alkali_flavonic acid A1 colloidal dioxin — 1.2 2.8 75 Invention Example 26 ΑΙΛ Powder Sift Powder — 1.2 1.6 * 75 Intersection Example *: Suspended in alcohol with a viscosity of 1.6 and spray-coated 312XP / Invention Manual (Supplement) / 94-03 / 93137129 4] 200525042 Table 6

No. Sequence of the annealing separator coating step (before / after recrystallization annealing) Coatable annealing separator Adhesive peeling amount (g / m) Annealing separation effect Peel strength (N) Remark 1 After 〇X 1.10 〇0 After Comparative Example 2 After OX 1.05 〇0 Comparative Example 3 Before OX 1.05 X 65 After Comparative Example 〇X 1.10 〇0 Comparative Example 4 Before 〇X 1.10 Δ 50 After Comparative Example 〇X 1.00 〇 After Comparative Example 5 After 〇00 X 90 Comparative Example 6 Before 0.000 005 After Invention Example 005 005 Invention Instance 7 Before 0.000 002 After Invention Instance 0.000 003 Invention Instance 8 After 0000 002 Famous Example 9 After 00 00 Inventive Example 10 After 2000 0 Introductory Example 11 After 0 000 OO 0 Inventive Example 12 Before 0 Δ 0.80 0 After Inventive Example 0 Δ 0.75 0 Inventive Example 13 After 0000 〇 Inventive Example 14 After X 〇 0 Δ 20 Comparative Example 15 After Δ 〇 0 〇 0 Comparative Example 16 After 〇 0.15 〇 0 Inventive Example 17 After 〇 Δ 1.5 〇 Comparative Example 18 After 0000 OO 0 Inventive Example 19 After X 〇0 Δ 40 Comparative Example 20 After 〇00 〇0 Example 21 After 0000 0 Inventive Example 22 After 0000 0 Inventive Example 23 After 0000 0 Inventive Example 24 After 0000 Inventive Example 25 After 0000 Inventive Example 26 Before XX After 1.0 X 70 Comparative Example 〇 1.0 1.0 Comparative Example 42 3] 2XP / Invention Specification (Supplement) / 94-03 / 93] 37] 29 200525042 Table

No. ------ Ί__ The sequence of the annealing separator coating step (before / after recrystallization annealing) Bs (T) Wl7 / 5〇 (W / kg) Tensile resistance to bending and peeling Minimum minimum bending radius (mm) Red Aluminum ferrite t (second heart (after mass annealing) and annealed ppm) Remark A1 NCS Se 6 1.90 1.03 25 5 < 5 10 < 4 < 10 Invention Example 7 〇 1.1.91 1. 03 30 5 < 5 5 < 4 < 10 Inventive Example 8 r \ after 1.92 0.98 30 8 < 5 10 5 < 10 Inventive Example 9 after 1.91 1.03 25 9 < 5 8 < 4 < 10 Inventive Example 10 after 1.92 0.99 30 5 < 5 8 6 < 10 Invention Example 11 After 1 η 1.92 0.97 30 7 < 5 6 5 < 10 Invention Example 13 L_ After 1.90 1.05 35 5 < 5 10 < 4 < 10 Invention Example 16 — After 1.89 1.06 30 8 < 5 8 < 4 < 10 Invention Example 18 After 1.90 1.04 25 9 < 5 13 < 4 < 10 Invention Example 20 After 1.91 1.04 30 5 < 5 15 5 < 10 Inventive Example 21 after 1.90 1.05 30 6 < 5 11 < 4 < 10 Inventive Example 22 after 1.89 1.05 25 6 < 5 6 < 4 < 10 Inventive Example 23 after 1.90 1.03 30 8 < 5 7 5 < 10 Invention Example 24 After 1.91 1.02 30 8 < 5 9 5 < 10 Invention Example 25 1.91 1.02 25 7 < 5 9 < 4 < 10 invention (Example 2) prepared according to the following method has an excellent forsterite film of grain-oriented electrical steel sheet and magnetic properties of the. Manufactured by a continuous casting method containing C: 0.019mass%, Si: 3.28mass%, Mn: 0.073mass%, and Sb: 330massppm, and contains suppressed contents to A1: 38massppm, N: 30massppm, S: 18massppm, and Se: Flat steel slabs less than 10 masspp in (within less than the analytical limit) and without inhibitor-forming components. Here, the remainder is iron and unavoidable impurities. After heating the flat steel blank at 120 ° C, hot-rolled steel sheet having a sheet thickness of 2.0 mm was processed by hot rolling, and the hot-rolled steel sheet was annealed at 1050 ° C for 60 seconds. Next, cold-rolled steel sheets with a sheet thickness of 0.30 mm were cold-rolled and recrystallized and annealed in a dry environment at a dew point of 45 ° C at 90 ° C for 10 seconds. After recrystallization annealing, the first batch annealing is performed. Annealing separation 43 312XP / Invention Specification (Supplement) / 9 '03 / 93137〗 29 200525042 The agent was applied before or after recrystallization annealing as shown in Table 8. The application of the annealing separating agent is performed using a roll coater, and then it is fired at a temperature of 250 ° C and allowed to cool. The roasting is performed by propane gas direct fire roasting. The first batch annealing was carried out under a nitrogen atmosphere at 86 5 ° C for 50 hours to complete the secondary recrystallization. Then, investigate the coating properties of the annealing separator, the adhesiveness of the dried annealing separator after drying, and the annealing separation effect after the first batch annealing. For the samples with good results, follow the subsequent steps to prepare Finished boards. In the subsequent steps, first, continuous annealing is performed to form a good internal oxide film, and then an annealing separator containing MgO as a main component is applied. Since the first batch annealing is performed in a state where C remains at 100 to 150 m a s s p p m, decarburization is also performed at the same time when continuous annealing is performed to form an internal oxidation film. Continuous annealing is performed in an oxidizing environment at a dew point of 60 ° C at 80 ° C for 80 seconds. In addition, an annealing separator is used which contains MgO: 92.5 mass% and Ti〇2: 7. 5 Mass% is the solid content. Second, the second batch annealing is performed. According to the steel composition of this example, the high temperature annealing around 1 200 ° C required for the purification of the inhibitor components is not required. As long as it is a condition that can form a forsterite film. Therefore, in the second batch annealing, it is maintained for 5 hours at 1 100 t lower than the conventional setting, and the environment is maintained. It is set to dry hydrogen. Next, coating, baking, and stress relaxation annealing of the tension film are performed at the end. The tension film is made of phosphoric acid, chromic acid, and colloidal silicon dioxide, and is fired at 800 ° C. The stress relaxation annealing is carried out under the conditions of maintaining at 800 ° C for 3 hours in a nitrogen atmosphere. 44 3 12XP / Invention Specification (Supplement) / 94-03 / 93137129 200525042 Composition and coating The conditions are the same as in Example 1 and correspond to No. shown in Table 5. Table 8 shows the sequence of the separation agent coating steps (before and after recrystallization annealing), the coatability of the annealing separation agent, the density of the annealing separation agent after drying, and the annealing separation effect after the first batch annealing. As in Example 1, for the steel made by the method of the present invention, regardless of the order of the annealing release agent cloth, good coating properties of the annealing release agent and the adhesion of the annealing release agent after drying and The separation effect after the first batch annealing. From this table, it can be seen that the annealing separator of the present invention is effective even if it does not contain an inhibitor. Table 9 shows that the subsequent steps are applied to the annealing applied to the present invention The magnetic characteristics, forsterite texture, and A 1, C, N, S, and S e contents after the second batch annealing in the case where a finished plate is prepared by dividing the sample. The same. In the case of applying the annealing separating agent within the scope of the present invention, the balance between the properties and the characteristics of the forsterite film is achieved, and the concentration of impurities is also a problem. 3 12XP / Invention Specification (Supplement) / 94 -03/93137129 The adhesion of the coating t, annealing for dry film from each of Unexamined Patent Laid-magnetic not 200,525,042 in Table 8

No. Sequence of annealing separator coating steps (before / after recrystallization annealing) Coatable annealing separator Adhesive peeling amount (g / rri) Annealing separation effect Peel strength (N) Remark 1 Before 〇X 1.15 Δ 45 After Comparative Example 0 × 1.00 0 Comparative Example 2 Before 0 × 1.00 Δ 35 After Comparative Example 0 × 1.00 0 Comparative Example 3 After 0 × 1.05 0 Comparative Example 4 After 0 × 1.15 0 Comparative Example 5 After 0 × 0 X 60 Comparative Example 6 After 0000 〇3 Inventive Example 7 After 0000 〇3 Inventive Example 8 〇 0 '0 〇3 After Inventive Example 〇 0 〇 2 Inventive Example 9 前 〇 00 〇 0 After Inventive Example 〇00 〇0 Inventive Example 10 after 0000 〇0 Inventive Example 11 after 0000 〇0 Inventive Example 12 after 〇Δ 0.8 〇0 Inventive Example 13 after 0000 〇0 Inventive Example 14 before X 〇 Δ 40 After Comparative Example X 〇 0 Δ 25 After Comparative Example 15 After Δ 〇 0 〇 0 Comparative Example 16 after 〇 〇 0.2 〇 0 Invention Example 17 After 〇 Δ 2 〇 Comparative Example 18 After 〇 00 〇 0 After Invention Example 19 After X 〇 0 Δ 35 Comparative Example 20 and later 00 Example 0 Invention Example 2 1 After 0000 0 Inventive Example 22 After 0000 0000 Inventive Example 23 After 0000 Inventive Example 24 After 0000 Inventive Example 25 After 0000 Inventive Example 46 312XP / Invention Specification (Supplement) / 94-03 / 93】 3 7129 200525042 Table

No. 〇t contains -1 withdrawal: ί pm) Anneal release agent Fenbu step forward; before / after recrystallization annealing) ~~ 72_ Bs (T) W17 / 50 (W / kg) bending resistance peeling resistance minimum bending Radius (_) in red aluminum and iron: (after the second batch of 5) (inassi: ϊ Note A1 NCS Se Ό 7 after ^ l.9l 1.01 25 10 < 5 10 10 < 10 Invention Example 0 € ^ l 90 1.02 25 9 < 5 12 11 < 10 Invention Example 0 9 10 _ HZ ----_ 1.92 0.99 30 8 < 5 5 8 < 10 Invention Example 1-1.91 1.03 25 9 < 5 6 10 < 10 after the invention example 1. 92 0.99 30 9 < 5 5 12 < 10 invention example 11 Ί '1.92 0. 98 25 11 < 5 8 11 < 10 invention example 13 1 η 1.90 1.04 30 11 < 5 9 10 < 10 @ 明 例 lb-€ ^ 1.89 1.05 30 14 < 5 13 12 < 10 Invention Example 18 20 __, Γ ------- 1.90 1.04 30 9 < 5 8 12 < 10 Inventive Examples-Later 1 1.90 1.05 25 13 < 5 11 12 < 10 Inventive Examples 21 1.91 1.03 25 15 < 5 9 11 < 10 Inventive Examples 22 23 1.91 1.03 30 16 < 5 5 13 < 10 Invention After example 1.91 1.03 30 12 < 5 6 12 < 10 Invention Example 24 lZ I — 1.90 1.05 25 11 < 5 6 9 < 10 rounds Example 25 1.91 1.04 30 14 < 5 7 11 < 10 Inventive Example (Example 3) A grain-oriented electrical steel sheet having no forsterite film and excellent magnetic properties and processability was produced according to the following method. Continuous casting Production method contains C: 0.020mass%, Si ·· 3.31mass%, M η: 0 · 〇6 〇mass%, and S b: 4 5 0 mass ρ ρ πι, and the inhibitor-forming component contains Al: 300 niassppm and N : 70massppm, and the remainder is a flat steel blank composed of iron and unavoidable impurities. After heating the flat steel slab at 120 ° C, the hot-rolled steel sheet having a plate thickness of 1.8 mm was processed by hot rolling, and the hot-rolled steel sheet was annealed at 95 ° C for 60 seconds. Next, the cold-rolled steel sheet with a sheet thickness of 0.27 ιη η! Was subjected to recrystallization annealing in a dry environment with a dew point of 45 ° C at 880 ° C for 10 seconds. , And then post-processing annealing. The annealing separator was applied before or after recrystallization annealing as shown in Table 10. The coating is carried out using a roll coater and is applied at a plate temperature of 250 ° C. 47 312XP / Invention Specification (Supplement) / 94-03 / 93137129 200525042 After baking, it is allowed to cool. The roasting is performed by propane gas direct fire roasting. During post-processing annealing, it was maintained at 860 ° C in a N 2 environment for 4 5 hours to achieve secondary recrystallization, and then maintained at 12 0 ° C in a Η 2 environment for 5 hours to perform purification. The components and application conditions of the annealing release agent were the same as those in Example 1, and were performed in accordance with the conditions corresponding to each N 0. Then, investigate the coating properties of the annealed release agent, the adhesiveness of the annealed release agent after drying, and the effect of the annealed separation after the post-processing annealing. For the samples with good results, further steps are performed to make the finished board . In the subsequent steps, coating, firing, and stress relaxation annealing of the insulating film are performed. The insulating coating is a chromate system containing organic resins, and is fired at 300 ° C. The stress relaxation annealing was performed under a nitrogen atmosphere at 750 ° C for 2 hours. Table 1 0 shows the coating properties of the annealing separator, the adhesiveness of the annealing separator after drying, the annealing separation effect after the post-processing annealing, the magnetic characteristics, the characteristics of the insulation film, and the A, C, and N after the post-processing annealing. , S, Se content. Since the viscosity of the annealing separator is outside the scope of the present invention, the coating properties are significantly poor, and the steel plates are closely adhered to each other in the uncoated portion. In the cases of N. 12 and 15. Both the ratio of A 1 compound to S i compound are outside the proper range of the present invention. Since N. 0.1 2 has a small amount of the film-forming component A 1 compound, the annealing separating agent is The adhesion is poor. On the other hand, No. 15 has a large amount of highly reactive A 1 compounds, and the coating solution is unstable, so that a uniform film cannot be formed. As a result, the appearance is poor. Since the main components of the annealing separator are outside the scope of the present invention, the adhesion to the steel sheet is insufficient. No. 5 Due to insufficient coating amount of the annealing separator, 48 312XP / Invention Specification (Supplement) / 94-03 / 93137129 200525042 In the post-processing annealing, the steel plates are closely adhered to each other. Ν ο · 1 7 The peeling occurred due to insufficient coating of the annealed release agent and insufficient adhesion to the steel sheet. Nos. 1_1, 4-1, 5, 6_1, 14 and 19 cannot evaluate the magnetic properties and bending peel resistance because the steel plates are closely adhered to each other. No.1, 4, 6, 11, 1 and 16 are classified according to the coating sequence of the annealing separator, and are implemented before and after the recrystallization annealing. The annealing separation agent of the present invention is independent of the application order of the annealing separation agent, and can obtain good coatability of the separation agent, adhesion of the separation agent after drying, and annealing separation effect during post-processing annealing. It was found in Nos. 1 and 4 that are comparative examples that the annealing separation effect was different due to the different application order of the annealing separation agent. It is presumed that, for the same reason as in Example 1, there is a difference in the amount of annealed release agent attached when post-processing annealing occurs. Therefore, it was learned that those who applied the annealing separator according to the present invention showed good coatability of the annealing separator, adhesion of the dried separator after drying, annealing separation effect after post-annealing, magnetic properties, and insulation coating. Characteristics and purification of red aluminum and iron impurities. In particular, the film characteristics showed better characteristics than the forsterite film shown in Examples 1 and 2. From this, it can be known that the annealing separator of the present invention can also be favorably applied to a directional electromagnetic steel sheet of a type using an inhibitor that needs to be purified by high temperature annealing. 49 312XP / Invention Specification (Supplement) / 94-03 / 93] 37129 200525042 200525042 (Example 4) A grain-oriented electrical steel sheet having no forsterite film and excellent workability was prepared according to the following method. Production of non-containing inhibitors containing C: 0.018mass%,%, Mn: 0.070mass% and Sb: 300massppm, to A 1 · 40massppm, N: 25massppni, S: 1 5mas below 10 massppm by continuous casting The flat residue of the composition is iron and unavoidable impurities. The flat steel blank was then hot-rolled to a hot-rolled steel sheet having a thickness of 1.8 mm, and the hot-rolled steel sheet was annealed for 6 Q seconds. Next, the cold-rolled steel sheet processed by cold rolling is subjected to recrystallization annealing under the conditions of a dew point of 45 ° C in a dry environment, and then post-processing is performed. The annealing separator is recrystallized according to Table 11 Uncoated. The coating was carried out using a roll coater, and it was allowed to cool after firing at 250 ° C. When the roasting system is annealed with a propane gas direct fire roaster, it is recrystallized after being maintained in the N 2 environment at 875 ° C for 45 times, and then processed and annealed in the Ar environment at 1000 ° C. The amount of C in the decarburized annealed material is performed in an oxidizing environment. Then, as the components of the annealing separator and the coating conditions 1, the coating properties of the annealing separator, the release properties after drying, and the post-annealing properties were investigated in accordance with the No. corresponding to each of the No. shown in Table 5. The effect of annealing separation, the sample is further subjected to subsequent steps to make a finished plate 312XP / Invention Manual (Supplement) / 94-03 / 93137129 Magnetic properties and Si: 3. 32mass and suppressed content sppm and Se: steel Embryo. Here, the heating is performed at 1 200 ° C and the plate thickness is 0.35 mm at 850 ° C. 8 8 0 ° C X 10 seconds fire. Perform before or after the fire reaches the plate temperature. Add hours afterwards for two to five hours. After that, the reduction of red iron is carried out in accordance with the embodiment. Then the fire separation agent is denser than that with good results. 51 200525042 In the subsequent steps, coating, firing and stress relaxation annealing of the insulation film are performed. The insulating coating is a chromate system containing organic resins, and is fired at 300 ° C. The stress relaxation annealing is performed under a nitrogen atmosphere at 750 ° C for 2 hours.

Table 1 1 shows the coating properties of the annealing release agent, the adhesiveness of the annealing release agent after drying, the annealing separation effect after post-processing annealing, the magnetic characteristics, the characteristics of the insulating film, and the A, C, and N after post-processing annealing. , S, Se content. As in Example 3, good results can be obtained regardless of the application order of the steel and the annealing separator according to the present invention.

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Bu I 001 6ί b, 02 Ώ 6 (NurnIs / s-inch6 / ίρ} ®) _ ^? Ίι ^^ α; χ (ΝϊΓη 200525042 (Example 5) Apply the annealing separator as described in Table 12 To prepare a directional electromagnetic steel sheet. The manufacturing steps are shown in Table 13. Steps A and B (using the method of post-process annealing once) are applied in Example 3, Step C, and Step D (using the second batch annealing). The method) is to apply the flat steel blank and manufacturing conditions of Example 1. Regarding the annealing separator, the components other than the main component or the coating conditions are the same as those of Example 1. In addition, No. 6 is substantially not observed by the light scattering method. It is judged that the solution is essentially a solution to the scattering. The implementation results are shown in Tables 13 and 3. The annealing and separating agents of the present invention all show excellent results. The annealing and separating effect is particularly high when the Si compound is contained as a stable compound at high temperature. Among them, it is preferable to use the S i compound alone as a stable compound at a high temperature. That is, to use the colloidal solution S i compound alone in the same coating amount and viscosity as No. 1 to 5, 7 shown in Table 13 ( Colloidal silicon dioxide) Example 1 (N of Table 6) 1 3) or Example 3 (N ◦ · 1 3 in Table 10) showed the best characteristics, which is better than the results of this example shown in Table 13. Table 12

No. Coating amount of the main component of the separating agent (g / rri) Viscosity (mPa · s) Solid content ratio (mass%) of A1 compound A1 Compound stable at high temperature Other 1 acetic acid A1 colloidal dioxide; δ , Tift fine powder — 1.2 1.8 Al2O3 / (Al2〇3 + Si〇2 + Ti〇2): 50 2 alkaline acetic acid A1 colloidal dioxide crushing, Tift fine powder sulfuric acid Sr 1.2 1.8 Al2 03 / (Al2 〇3 + Si〇2 + Ti〇2): 50 3 acetic acid A1 colloidal Tia — 1.2 1.8 Α1 · 2〇3 / (Αΐ2〇3 + T1O2) · 60 4 acetic acid A1 colloidal Sr0, Ba0 — 1.2 1.8 Al2〇3 / (Al2a + SrO + M)): 70 5 acetic acid A1 CaO micropowder sulfuric acid Mg 1.2 1.8 Al2〇3 / (Al2〇3 + CaO) · 80 6 acetic acid A1 colloidal dioxide Silicon — 0.1 1.8 AWai ^ + Sift): 90 7 Alkaline acetic acid A1 Zirconium :, fine powder — 1.2 1.8 Α1Λ / (Α12〇3 + Zγ〇〇: 70 54 3 12XP / Invention Specification (Supplement) / 94-03 / 93137129 200525042 Table 13

No. Step 氺 Coating annealing release agent Adhesive f peeling amount (g / m) Annealing separation effect Peel strength (N) Be (T) W.7 / 50 (W / kg) Flexural peel resistance Minimum bending radius (mm) Content in red aluminum iron (post-processing annealing / second batch withdrawal, after fire (mass ^ 〇_.) A1 NCS Se / 1 Π 1 A 〇〇0 〇2 1.86 1.05 20 5 < 5 13 5 < 1U ^ π 2 A 〇〇0 〇2 1.89 1.02 20 6 < 5 13 < 4 1 < 1ϋ / 1 π 3-1 A 〇〇0 〇5 1.86 1.05 20 6 < 5 14 5 < ιυ η 3-2 B 〇〇0 〇6 1.85 1.06 20 5 < 5 JL · 5 < 10 --TΠΓ 4 C 〇〇0 〇5 1.91 1.03 30 9 < 5 JL · < ιυ ^ ΊΓ 5-1 C 〇〇0 〇 5 1.92 0.99 30 5 < 5 9 5-2 D 〇〇〇 〇4 1.92 0.99 30 8 < 5 9 5 < 10 6-1 A 〇〇0 〇r 3 1.85 1.07 20 6 < 5 15 5 < 10 6-2 C 〇〇0 〇3 1.90 1.05 30 6 < 5 9 ιΤ " '< 10 7-1 B 〇〇0 〇5 1.85 1.06 20 7 < 5 12 < 4 < iii 7-2 D 〇〇0 〇4 1.91 1.04 30 7 < 5 HJ < 4 < 1〇1 * A: Recrystallization annealing-coating of an annealing separator Post-processing annealing B: Coating of annealing separator—recrystallization annealing—post-processing annealing C: Recrystallization annealing—coating of annealing separator The first batch annealing ^ continuous annealing ~ the second batch annealing D : Coating of annealing separating agent-recrystallization annealing-► batch annealing for the first time-continuous annealing ~ batch annealing for the second time (Example 6)

The flat steel blanks having the composition described in Table 14 were manufactured from molten steel by a continuous casting method, and a grain-oriented electrical steel sheet was prepared in the same manner as in Example 5 in accordance with the classification in Table 15. However, the amount of C before secondary recrystallization was not specifically adjusted for No. 2 and the decarburization treatment was also omitted. In addition, for No. 1 and No. 7 systems, recrystallization annealing was performed in an oxidizing environment at a junction temperature of 30 C, and the amount of C in secondary re-, day-to-day and day-to-day annealing was adjusted to 100 ~ i50massppmo Anneal release agent and coating conditions are in accordance with NO 5 of Table 5. The results are shown in Table 15 below. Although the magnetic properties also depend on the components of the steel sheet ', each component achieves the desired magnetic properties. 55 312XP / Invention Specification (Supplement) / 94-03 / 9313 7129 200525042 Table 14

No. flat steel component C (mass%) Si (mass%) Μη (mass%) A1 (massppm) N (massppm) S (massppm) Se (massppm) Other (massppm) 1 0.075 3.2 0.05 40 40 20 < 10 2 0.003 3.2 0.05 300 i 80 20 < 10 3 0.015 2.1 0.04 310 75 20 < 10 4 0.02 7.8 0.05 43 i 37 20 < 10 Sn: 400 5 0.018 3.35 0.008 290 80 20 < 10 6 0. 020 3.15 0.065 50 38 20 < 10 7 0. 062 3.0 0.03 35 60 20 < 10 B: 25 8 0.015 5.0 0.04 30 30 20 150 9 0.015 3.05 0.05 35 40 150 < 10 Table 1 5

No. Step 氺 Coating annealed release agent adhesion ± ± Peeling amount (g / m) Filament peeling Grade 5 ⑻ Be (T) W coffee (W / kg) and minimum bending radius (mm) lffgi peelability Content in money (Xmassppn after strangling / second eclipse test) A1 NCS Se 1 -1 A 〇〇0 〇0 1.85 1.08 20 7 < 5 15 5 < 10 2-1 A 〇〇 0 〇0 1.82 1.16 20 6 < 5 13 < 4 < 10 3-1 A 〇〇— 0 〇0 1.87 1.15 20 5 < 5 13 < 4 < 10 1-2 B 〇〇0 〇0 1.85 1.07 20 5 < 5 12 < 4 < 10 2-2 C 〇0 〇0 1.82 1.08 30 9 < 5 7 6 < 10 3-2 D 〇 〇0 〇0 1.92 1.08 30 8 < 5 8 5 < 10 4 A 〇〇0 〇0 1.82 1.02 20 5 < 5 11 5 < 10 5 B 〇〇 〇0 1.85 1.06 Γ 20 5 < 5 14 6 < 10 6 C 〇〇〇 〇 0 1.91 r 1.03 30 7 < 5 9 6 < 10 7 C 〇〇〇 〇0 1.90 1.05 30 8 < 5 6 < 4 < 10 8 D 〇〇0 〇0 1.91 1.05 30 6 < 5 5 5 < 10 9 C 〇00 〇0 1.90 1.06 30 6 < 5 5 5 * A: Coating of recrystallization annealing annealing separating agent-post-processing annealing B: coating of annealing separating agent- Post-Crystal Annealing Process C ·· Recrystallization Annealing- > Application of Annealing Separator First Batch Annealing ^ Continuous Annealing ~ Second Batch Annealing D: Application of Annealing Agent-Recrystallization Anneal batch annealing for the first time-continuous annealing ~ batch annealing for the second time (industrial availability) The annealing separator for directional electromagnetic steel sheets according to the present invention has good coatability and tightness to steel sheets It can ensure stable operation in the coating process of annealing release agent and the subsequent steps. In addition, when achieving the same adhesion as 56 3UXP / Invention Specification (Supplement) / 9103/93137129 200525042, it also has excellent operability that does not hinder purification or decarburization, and does not require coating removal operations. By applying the annealing separating agent to the manufacturing steps of the directional electromagnetic steel sheet, it is easy to achieve a directional electromagnetic steel sheet excellent in both magnetic characteristics and forsterite coating characteristics and without a forsterite coating and in magnetic characteristics and Manufacture of grain-oriented electrical steel sheet with excellent workability.

57 312XP / Invention Manual (Supplement) / 94-03 / 9313 7129

Claims (1)

200525042 10. Scope of patent application: 1. An annealing method for a directional electromagnetic steel sheet, which is an annealing separator coated on the steel sheet, and the coated steel sheet is annealed, characterized in that the annealing separator is a solution or The state of the colloidal (c ο 1 1 〇id) solution contains an A1 compound, a compound which is stable at high temperature, and has a viscosity of 25 (m P a · s) or less. 2. The annealing method for grain-oriented electrical steel sheet according to item 1 of the patent application, wherein the annealing separator contains the above-mentioned stable compound at high temperature in the state of a solution or a colloidal solution. 3. For the annealing method of grain-oriented electrical steel sheet according to item 1 of the application, wherein the content of the A 1 compound is a solid content ratio expressed by the following formula (1) of 40 to 95 mass%: the solid content of the A 1 compound Ratio = (solid content of the above-mentioned A 1 compound) / {(solid content of the above-mentioned A 1 compound) + (solid content (and) of the above-mentioned stable compound at a high temperature) 丨 .. Formula (1) wherein the above-mentioned A 1 The solid content of the compound is converted into A 1 2 0 3, and the stable compound at the above-mentioned high temperature is converted into the main compound produced in the case of baking after the application of the annealing separator. 4. The annealing method for a grain-oriented electrical steel sheet according to item 1 of the scope of patent application, wherein the compound stable at high temperature is selected from the group consisting of Si compound, Sr compound, Ca compound, Zr compound, Ti compound, and B a compound is composed of at least one compound, and the content of the A 1 compound is a solid content ratio represented by the following formula (2) of 40 to 9 5 mass%: the solid content ratio of the A 1 compound = ( A 1 solid content of compound) / {(A 1 compound 58 312XP / Invention (Supplement) / 94-03 / 93137129 200525042 solid content of the substance) + (solid content of at least one of the above compounds ((2) here, The solid content of each compound is converted into the following compound values: A1 compound ... AI2O3; Si compound ... Si〇2; Sr compound ... SrO; Ca compound ... CaO; Z r compound .. .Z r 0 2; T i compound ... T i 0 2; B a compound ... B a 0. 5 · The method of grain-oriented electrical steel sheet according to item 4 of the patent application scope, wherein the annealing separator is There is at least one of the above compounds in a solution or a colloidal solution. The annealing method is to anneal cloth on a steel sheet and anneal the coated steel sheet, characterized in that the above-mentioned annealing separating agent converts the ratio of A 1 compound and Si compound to A1 compound and Si compound to Al203. / (Al2〇 value is 40 ~ 95mass%, viscosity is 25mPa · s or less, and the state of the colloid solution. 7. For the annealing method of the direction plate according to any one of the claims 1 to 6, the above-mentioned A The 1 compound is either one or both of the A 1 compound having a hydroxyl group and the A 1 water reactant having a hydroxyl group and an organic acid group. 8. For example, the directional electromagnetic steel sheet method of item 7 of the scope of patent application, wherein, The above A 1 compound is selected from the group consisting of test acetic acid A 1, A 1, test hydrochloric acid A 1, test lithocholic acid A 1, test oxalic acid A 1, 3] 2XP / Invention Specification (Supplement) / 94-03 / 93137129 and))} .. The state of the annealed side of the formula weight contains the main component of the separating agent coating, 3 + S ί 0 2) is an annealed side alkali which is a solution or a magnetic steel and organic acid compound Alkaline acid sulfamate 59 200525042 acid A 1, lactic acid A 1 and lemon Acid A one kind or two kinds of 1 to the mixture. 9. The annealing method for a directional electromagnetic plate according to any one of claims 1 to 6, in which the above-mentioned annealed separating agent is a solid content ratio obtained in accordance with the case of baking after the above-mentioned annealed separating agent is coated. Further, S or S-containing compounds are 25 mass% or less. 10. The annealing method for a grain-oriented electrical steel sheet according to item 9 of the application, wherein the S or S-containing compound is at least one selected from the group consisting of sulfuric acid Sr, sulfuric acid, and sulfurized Mg. 1 1. Use of a liquid as an annealing separator, the liquid system containing a compound A 1 in the state of a solution colloidal solution, and further containing a compound selected from the group consisting of S i compound, S r compound, Ca compound, Z r compound, T i If the compound is at least one compound of the group B a, the content of the above-mentioned A1 compound is represented by the following formula (2) with a solid content ratio of 4 to 95 mass% and a viscosity of 25 mPa · s or less: A 1 compound solid form Fraction ratio two (solid content of A 1 compound) / {(solid content of A 1 compound) + (solid content (and) of at least one of the above compounds) 丨 .. (2) Here, the solid content of each compound is Converted to the weight of each of the following compounds: A1 compound ... AI2O3; Si compound ... Si〇2; Sr compound ... SrO; Ca compound ... Ca〇; Z r compound ... Z r 0 2; T i compounds ... T i 0 2; B a compounds ... B a 0. 312XP / Invention Specification (Supplement) / 94-03 / 93137129 Shanggang Substance contains square Mg or chemical compound and combined amount 60 200525042 1 2. If the liquid in item 11 of the scope of patent application is used as an annealing separator, of which, The liquid system contains at least one of the above compounds in a state of a solution or a colloidal solution. 1 3. The use of a liquid as an annealing separator, the liquid system uses A 1 compound and Si compound as the main component, and the ratio of A 1 compound and Si compound is converted into Al2OJ (Al2〇3 + Si〇2 ) The value is 40 ~ 95mass%, the viscosity is 25 m P a · s or less, and it is in the state of a solution or a colloidal solution. 1 4. A method for manufacturing a grain-oriented electrical steel sheet, comprising: made of molten steel containing C: 0.08niass% WT, Si: 2.0 ~ 8.0mass%, Μη: 0. 0 0 5 ~ 1.0 mass% A step of rolling a flat slab into a final sheet thickness to form a steel sheet; applying a recrystallization annealing step to the above-mentioned steel sheet; and applying a batch method to the above-mentioned steel sheet by a method of any of claims 1 to 10 in the scope of patent application First batch annealing step of annealing; Here, the above-mentioned annealing separating agent applied before annealing in the first batch annealing step is referred to as a first annealing separating agent, and the recrystallization annealing is performed in the first annealing separation 0 0 5 before the application of the agent, or after the application of the first annealing release agent and before the batch annealing, and the coating amount per side of the first annealing release agent is set to 0. 0 0 5 ~ 5 g / m2, and has the step of applying continuous annealing to the above steel plate afterwards; applying a second annealing separator containing MgO on the above steel plate, and then applying the second batch annealing step of batch annealing. 1 5. According to the method of manufacturing patented directional electromagnetic steel sheet No. 14 in the scope of patent application 61 312XP / Invention Specification (Supplement) / 94-03 / 93137] 29 200525042 method, wherein the above-mentioned flat embryo has A flat embryo made of molten steel having a content lower than 150 ppm and a content of N, S, and Se reduced to 50 ppm or less. 16. The method for manufacturing a grain-oriented electrical steel sheet according to item 14 or 15 of the scope of patent application, wherein the step of rolling the flat billet to the final sheet thickness to make the steel sheet includes: applying hot rolling to the flat billet. A step of making a hot-rolled steel sheet; if necessary, applying a step of annealing the hot-rolled steel sheet to anneal the above-mentioned hot-rolled steel sheet; and applying cold rolling once or performing cold rolling more than two times with intermediate annealing to make a final Steps for plate thickness. 1 7. A method for manufacturing a directional electromagnetic steel sheet, characterized in that: it is made of flat steel made of dazzling steel containing C: 0.08mass% or less, Si: 2.0 ~ 8.0mass%, Μη: 0.005 ~ l.Omass% A step of rolling a blank to a final thickness to make a steel sheet; a step of applying recrystallization annealing to the above-mentioned steel sheet; and applying batch annealing to the above-mentioned steel sheet by a method according to any one of claims 1 to 10 Annealing step; Here, the recrystallization annealing is performed before the application of the annealing separator in the post-processing annealing step, or after the application of the annealing separator and before the batch annealing, and the annealing is set. The coating amount of each side of the separating agent is 0.05 to 5 g / in2. 1 8. According to the method of manufacture of directional electromagnetic steel sheet No. 17 in the scope of patent application 62 3] 2XP / Invention Specification (Supplement) / 94-03 / 93137129 200525042 method, wherein the flat embryo is used to make A1 content A flat embryo made of molten steel having a composition reduced to 150 ppm or less and each content of N, S, and Se to 50 ppm or less. 19. The method for manufacturing a directional electromagnetic steel sheet according to item 17 or 18 of the scope of patent application, wherein the step of rolling the flat billet to a final sheet thickness to form a steel sheet includes: applying hot rolling to the flat billet. The step of making hot-rolled steel sheet; the step of annealing the hot-rolled steel sheet to anneal the hot-rolled steel sheet as needed; applying the cold rolling once, or performing two times of cold rolling with intermediate annealing to make the final sheet Thick steps. 2. A method for manufacturing a directional electromagnetic steel sheet, comprising: for a flat blank made of a dazzling steel containing C: 0.08 mass% or less, Si: 2.0 to 8.0 niass%, Mn: 0.005 to l. Omass% A step of applying hot rolling; secondly, applying cold rolling once, or performing two or more cold rolling sandwiching intermediate annealing to form a final sheet thickness; followed by a step of recrystallization annealing; and, The post-processing annealing step is performed by the method in the patent application No. 6; and the coating amount of the annealing release agent applied before the annealing in the above-mentioned post-processing annealing is set to 0. 0 0 5 to 5 g per side. m2. 2 1. A method for manufacturing a grain-oriented electrical steel sheet, comprising: for C: 0.08 mass% or less, Si: 2.0 to 8.0 mass%, "11: 〇.〇〇5 ~ 1.〇1 丨 1333% And has a component composition that reduces the content of eight 1 to 15 (^ 0 丨 11 or less 63 312XP / Invention Specification (Supplement) / 94-03 / 93137129 200525042 and reduces the content of N, S, Se to less than 50ppm The flat blank made of steel is subjected to hot rolling; secondly, cold rolling is applied once, or cold rolling is performed twice or more with intermediate annealing to form a final sheet thickness; followed by recrystallization annealing Zhixiang Township; and, followed by the step of post-process annealing by the method of the 6th scope of the patent application; In addition, the coating amount of the annealing separator applied before the annealing in the post-processing annealing is set to 5 to 5 g / m 2 per one side. 64 3 12XP / Invention Specification (Supplement) / 94-03 / 93] 37129 200525042 VII. Designated Representative Charts ... (1) The designated representative map in this case is: (). (2) Brief description of the component symbols in this representative figure: None 8. If there is a chemical formula in this case, please disclose the chemical formula that can best show the characteristics of the invention: None 312XP / Invention Specification (Supplement) / 94-03 / 93137129