Classifications

• • C—CHEMISTRY; METALLURGY
  • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
  • C22C—ALLOYS
  • C22C38/00—Ferrous alloys, e.g. steel alloys
  • C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
• • C—CHEMISTRY; METALLURGY
  • C21—METALLURGY OF IRON
  • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
  • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
  • C21D8/12—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of articles with special electromagnetic properties
  • C21D8/1277—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of articles with special electromagnetic properties involving a particular surface treatment
  • C21D8/1283—Application of a separating or insulating coating
• • C—CHEMISTRY; METALLURGY
  • C21—METALLURGY OF IRON
  • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
  • C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
  • C21D9/46—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for sheet metals
• • C—CHEMISTRY; METALLURGY
  • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
  • C22C—ALLOYS
  • C22C38/00—Ferrous alloys, e.g. steel alloys
  • C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
• • C—CHEMISTRY; METALLURGY
  • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
  • C22C—ALLOYS
  • C22C38/00—Ferrous alloys, e.g. steel alloys
  • C22C38/60—Ferrous alloys, e.g. steel alloys containing lead, selenium, tellurium, or antimony, or more than 0.04% by weight of sulfur
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
  • H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
  • H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
  • H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
  • H01F1/12—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials
  • H01F1/14—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials metals or alloys
  • H01F1/16—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials metals or alloys in the form of sheets

Definitions

• the present invention relates to an annealing separator for preventing seizure of grain-oriented electrical steel sheets during annealing, and an annealing method using the same for IJ.
• the present invention also relates to a method for producing a grain-oriented electrical steel sheet utilizing the annealing separator.
• a forsterite coating is applied to the grain-oriented electric steel sheet.
• grain-oriented electrical steel sheet is a steel sheet that achieves particularly excellent low iron loss by highly accumulating the crystal orientation in the ⁇ 110 ⁇ and 001> orientations called the Goss orientation.
• iron loss properties are regarded as important because they directly lead to the energy consumption of products.
• punchability and bendability are also important properties. That is, when manufacturing an iron core for a transformer or a rotating machine, the electromagnetic steel sheet is formed into a predetermined shape through processing such as punching and shear bending. Also, when a steel strip passes through a processing line for performing these processing, the steel sheet may be bent. Therefore, the above characteristics are important.
• grain-oriented electrical steel sheets are manufactured by processes disclosed in, for example, paragraph [0005] of JP-A-2003-41323. That is, the steel sheet obtained by rolling is subjected to recrystallization annealing, and then to one batch annealing called finish annealing. This batch annealing promotes secondary recrystallization, and accumulates Goss-directional crystal grains.
• the steel sheet is heated in a coil shape.
• Finish annealing for producing electrical steel sheets generally requires a high temperature, S, so that the steel sheets are seized in the coil.
• S a high temperature
• a technique of applying an annealing separator containing MgO as a main component and forming a funal stellite coating at the time of annealing is widely used. Fuorusuteti DOO quality coating and MgO in the annealing separating agent, during S i 0 2 and is believed to be formed by the reaction (although the coating film of the oxide formed on the surface of the steel sheet Fe Are also included).
• This forsterite coating has good annealing separation performance and also has an advantage in the properties of directional magnetic steel sheets.
• a hard coating tensile coating
• low iron loss can be achieved by applying tension to the steel sheet.
• the grain-oriented electrical steel sheet having the forsterite coating is inferior in both punching properties and bending properties.
• the die for punching is worn out quickly and burrs are generated on the O-sheared surface of the steel sheet.
• peeling is likely to occur even when bending and bending, good bending and peeling resistance that does not peel even when bending and the like are applied after strain relief annealing, for example, is required.
• a method of changing the component of the annealing separating agent i.e., an annealing separator containing no MgO which reacts with Si0 2 steel plate surface, recrystallization; applied after 3 ⁇ 4 blunt, the finish annealing Application methods have been attempted.
• the annealing separating agent containing as a main component other than MgO include alumina disclosed in JP-A-6-136448, JP-A-7-118750 and JP-A-5-156362. (Powder) as a main component, and those containing alumina and / or silicium as a main component disclosed in JP-A-11-61261 and JP-A-8-134542. ing.
• annealing separators are applied electrostatically or as a suspension in water slurry or alcohols to the steel sheet.
• these annealing separators have poor adhesion to steel sheets, they tend to peel off during the production line after application of the annealing separator. As a result, 1) it is difficult to control the amount of coating. 2) The yield of the annealing separator is poor. 3) There were problems such as the generation of dust and concerns about line contamination.
• an annealing separator having excellent adhesiveness to a steel sheet an annealing separator mainly composed of an aggregate of colloidal alumina in a feather form is disclosed in Japanese Patent Application Laid-Open No. 10-121142. ing.
• JP-A-2003-41323 discloses a technique for achieving both the magnetic properties and the film properties by performing two patch annealing steps after continuous re-annealing after recrystallization annealing. Is disclosed.
• the present invention has been made to solve the above-mentioned problems, and does not contain MgO, has excellent coatability to a steel sheet and excellent adhesion after coating, and causes a dust problem and a resulting line contamination. It proposes an annealing separator that can produce grain-oriented electrical steel sheets without any problem, and an annealing method using it.
• the present invention also relates to a method for producing a grain-oriented electrical steel sheet suitable for an iron core material of a transformer or a rotating machine, using the annealing separator.
• it proposes a method of manufacturing a grain-oriented electrical steel sheet with excellent coating properties of forsterite coating and a method of producing a grain-oriented electrical steel sheet with excellent workability without a phono-resterite coating. It is.
• the embodiments of the present invention include (1) a method of annealing a grain-oriented electrical steel sheet, (2) a use as an annealing separator, (3) a method of producing a grain-oriented electrical steel sheet having a forsterite coating, and (4) It is classified as a method of manufacturing grain-oriented electrical steel sheets without forsterite coating.
• the present invention is a.
• a method for annealing a grain-oriented electrical steel sheet comprising applying an annealing separator to a steel sheet and annealing the coated steel sheet, wherein the annealing separator contains an A1 compound in the form of a solution or a colloid solution, and A method for annealing a grain-oriented electrical steel sheet, comprising a compound stable at high temperatures and having a viscosity of 25 mPa's or less.
• a compound that is stable at high temperatures means that the compound does not react with or hardly reacts with the steel sheet surface or oxides on the steel sheet surface during the target annealing, and that the compound itself does not react or reacts. It is hard to wake up.
• at least one selected from the group consisting of Si compounds, Sr compounds, Ca compounds, Zr compounds, Ti compounds and Ba compounds is exemplified.
• MgO alone is stable at high temperatures, it does not fall under “high-temperature stability” as it reacts with oxides on the steel sheet surface.
• the A1 compound is in a solution state or a colloid solution state, a substance having a structural part (functional group or the like) having an affinity for a solution or a liquid forming the colloid solution (collectively referred to as a solvent for convenience). It is. Therefore, it is a substance that is chemically different from, for example, general slurry and alumina particles used in suspensions. Needless to say, even in the form of existence, it is different from slurry or suspension To do.
• the solvent is water-based.
• the A1 compound is at least one of an A1 compound having a hydroxyl group and an organic acid group, and a dehydration reaction product (including a partial dehydration reaction product) of the A1 compound having a hydroxyl group and an organic acid group.
• the A1 compound is a basic acetic acid Al, a basic formic acid Al, a basic hydrochloric acid Al, a basic nitric acid Al, a basic oxalic acid, a basic sulfamic acid Al, a basic lactic acid A1 and a basic quinone One or a mixture of two or more selected from the acids A1.
• the annealing separator may contain the compound stable at a high temperature in the form of a solution or a colloid solution. Further, the content of the A1 compound is 40 to 95 mass ° / in terms of a solid content ratio represented by the following formula (1). It is preferable that
• Solid content ratio of A1 compound (Solid content of A1 compound) / ⁇ (Solid content of A1 compound) + (Solid content (sum) of compound stable at high temperature) ⁇ Formula (1)
• the present invention preferably comprises
• a method for annealing a grain-oriented electrical steel sheet comprising applying an annealing separator to a steel sheet and annealing the coated steel sheet,
• the annealing separator contains the A1 compound in the form of a solution or a colloid solution, and at least one selected from the group consisting of Si compound, Sr compound, Ca compound, Zr compound, Ti compound and Ba compound.
• One type of compound is further contained, and the content of the A1 compound is 40 to 95 mass / ° in a solid content ratio represented by the following formula (2).
• a viscosity of the annealing separating agent is 25 niPa ⁇ s or less.
• Solid content ratio of A1 compound (solid content of A1 compound) / ⁇ (solid content of A1 compound) + (previously described solid content of at least one compound (sum)) ⁇ Formula (2) Wherein the solids content of the compound is converted value to the weight of each compound of the following A1 compound ⁇ ⁇ ⁇ ⁇ 1 2 0 3, Si compound ⁇ ⁇ 'Si0 2,
• the annealing separating agent may include at least one compound selected from the group consisting of the Si compound, the Sr compound, the Ca compound, the compound, the Ti compound and the Ba compound, in the form of a solution or a colloid solution. It may be contained in a state.
• a particularly preferred embodiment of the invention is a method for annealing a grain-oriented electrical steel sheet, comprising applying an annealing separator to a steel sheet and annealing the coated steel sheet, wherein the annealing separator is an A1 compound and a Si compound.
• the annealed separating agent further has a solid content ratio of 25 ma SS // which is required when the annealed product containing S or S is baked after applying the annealed separating agent.
• the “S or S-containing compound” is preferably at least one selected from Sr sulfate, Mg sulfate and Mg sulfide.
• the present invention provides an A1 compound in the form of a solution or a colloid solution, and at least one compound selected from the group consisting of a Si compound, an Sr compound, a Ca compound, a Zr compound, a Ti compound and a Ba compound.
• the liquid further contains: the content of the compound A1 is 40 to 95 mass ° / in terms of a solid content ratio represented by the above formula (2). And a liquid having a viscosity of 25 mPa's or less is used as an annealing separator.
• the annealing separator contains at least one compound selected from the group consisting of the Si compound, the Sr compound, the compound, the Zr compound, the Ti compound, and the Ba compound in the form of a solution or a colloid solution. May be.
• the present invention also includes a main component A1 compound Contact Yopi Si compound, 40 ⁇ 95Mass% in value ratio in terms of Al 2 0 3 / (A1 2 0 3 + Si0 2) of the A1 compound and Si compound And a liquid having a viscosity of 25 mPa's or less and being in the form of a solution or a coid solution is used as an annealing separator.
• the preferred annealing separator used in the method for annealing a steel sheet according to (1) is applicable to all the inventions of (2).
• the recrystallization annealing is performed either before the application of the first annealing separator or after the application of the first annealing separator and before the batch annealing. And the amount of application of the first annealing separator on one side is 0.005 to
• the grain-oriented electrical steel sheet has excellent magnetic properties and forsterite coating properties. (4) A method for producing a grain-oriented electrical steel sheet having no forsterite coating
• the recrystallization annealing is performed before the application of the annealing separating agent in the finish annealing step, or is performed after the application of the annealing separating agent according to (1) and before the patch annealing.
• This grain-oriented electrical steel sheet has excellent magnetic properties and workability.
• the invention can be applied to a grain-oriented electrical steel sheet that does not use an inhibitor-forming component.
• the slab is a slab made of molten steel having a composition in which A1 is 150 ppm or less and N, S, and Se are each reduced to 50 ppm or less.
• the step of rolling the slab to a final thickness to form a steel sheet includes: a step of hot-rolling the A1 slab to form a hot-rolled steel sheet; A step of performing hot-rolled sheet annealing to anneal the hot-rolled steel sheet as necessary, and a step of performing one or more cold-rolling operations including one or more intermediate-annealing processes to obtain a final thickness. And preferably
• a further preferred form of the invention of (4) is:
• 0mass 0/0 includes and 150ppm or less of Al Oyopi N, S Hot rolling of a slab made of molten steel having a composition of 50 ppm m or less, and then two or more cold rollings with one cold re-rolling or intermediate annealing An annealing separator applied to the final sheet thickness, followed by recrystallization annealing, and then subjected to finish annealing by the annealing method described in (1), and is applied before the annealing in the finish annealing.
• This is a method for producing a grain-oriented electrical steel sheet, wherein the coating amount is 0.005 to 5 g / m 2 per side.
• the annealing separator is mainly composed of A1 compound and S i compound, the Al 2 0 3 / (A1 2 0 3 + Si0 2) the ratio of the A1 compound and Si compound
• the converted value is 40 to 95 mass. /. It is preferable that the viscosity is 25 mPa's or less and that the solution is in the form of a solution or a colloid solution.
• the inventors of the present invention have conducted intensive studies on an annealing separator having excellent coatability and adhesion after coating.As a result, the inventors first found that the A1 compound and the compound stable at high temperatures were the main components, and at least the A1 compound was It has been found that the above-mentioned problems can be solved by using a solution state or a colloid solution state.
• the present inventors have also found a suitable viscosity of the annealing separator, a solid content ratio of the A1 compound, and a suitable coating amount when applied to a steel sheet. The present invention will be described below based on experiments that have succeeded.
• an aqueous colloid solution (solid content: 3.0 ma SS %) of silica sol (colloidal silicic power) was used as an annealing separating agent, and the surface of the steel sheet (both sides) was 0.1 ... 3. Coating was performed using a roll coater in the range of Og / m 2 .
• the steel sheet was baked at the ultimate temperature of 250 ° C and then allowed to cool.
• the applied amount of the annealing separator was determined from the difference in the weight of the steel sheet before and after the baking treatment, and this was used as the applied amount of the annealing separator.
• the specimen was kept at 850 ° C for 30 hours in a nitrogen atmosphere, and then kept at 1000 ° C for 5 hours in an Ar atmosphere.
• the obtained steel sheet was tested for three items: the applicability of the annealing separator, the adhesion of the annealing separator after drying, and the annealing separation effect during finish annealing.
• the details of each performance evaluation method are as follows. The same applies to the evaluation methods in Experiments 2 and 3 described later and the examples.
• the steel sheet after the application of the annealing separator was visually evaluated.
• the steel plate After baking the annealing separator, the steel plate was washed with running water at a flow rate of about 1. Om / s for 10 seconds while brushing the steel sheet. Then, it was drained with a ringer roll and dried under the condition of 200 ⁇ X10Os. Then, the weight of the steel sheet was re-measured, and the adhesion amount of the annealing separator was calculated again. Then, the difference between the amounts of the adhesion of the annealing separator before and after the water washing was determined, and this was defined as the amount of peeling. Based on the obtained peeling amount, the following evaluation was made.
• Separation amount of separating agent is 10% or less of applied amount
• Separation amount of separating agent is more than 10 to less than 80% of applied amount
• the separation amount of the separating agent is 80% or more of the applied amount • Annealing separation effect
• peeling strength was measured to evaluate as follows.
• silica sol had an annealing separation effect at the time of finish annealing, but had a problem in adhesion to a steel sheet as an annealing separating agent. Therefore, the present inventors examined the effectiveness of using alumina sol as a film-forming component in order to use silica sol as an annealing separating agent and to improve adhesion to a steel sheet.
• the ratio of the alumina sol and silica sol, in the range of. 20 to 100 mass% with A1 2 0 3 Pas Al 2 0 3 + Si0 2) in terms of the viscosity of the annealing separator is in the range of 3. 5 ⁇ 100 mPa 's, respectively change I let it. Note that the viscosity of the annealing separator was changed by using alumina sols having different viscosities.
• the viscosity of the alumina sol can be controlled by, for example, the shape of the sol particles and the solid content concentration.
• the viscosity will be high, and if it is close to spherical (or granular) or elliptical (or rod-like), the viscosity will be low.
• Table 2 shows the experimental results when the ratio between the alumina sol and the silica sol was changed. When the ratio of alumina sol was low, the adhesion of the annealing separator was insufficient. On the other hand, if the ratio of the alumina sol was too large, the film-forming effect was too strong, and it was difficult to apply uniformly to the steel sheet, resulting in poor appearance of the product. The effect of annealing separation was good under all conditions.
• Table 3 shows the experimental results when the viscosity of the annealing separator was changed. When the viscosity was increased, the applicability to the steel sheet was significantly deteriorated, and some portions were applied and some were not. Since the steel sheet seized in the area where the coating was not performed, it was found that the viscosity had to be controlled in order to secure good coating properties and to have an annealing separation effect. Table 2
• an annealing separator solid content concentration consisting of an aqueous colloid solution containing alumina sol and silicic acid sol as main components was used. 2.5 m ass %) was applied under each condition that the application amount was in the range of 0.001 to 6 g / m 2 per one side.
• the viscosity of the annealing separator was set to 2.5 mPa's, the ratio of the alumina sol and silica sol was 75 mass% in the A1 2 0 3 / (Al 2 0 3 + Si0 2) terms.
• the steel sheet was baked at the ultimate temperature of 250 ° C and allowed to cool. Then, as in Experiment 1, finish annealing was performed at 850 ° C for 30 hours in a nitrogen atmosphere and then at 1000 ° C for 5 hours in an Ar atmosphere.
• the obtained steel sheet was examined for three items: the coatability of the annealing separator, the adhesion of the annealing separator after drying, and the annealing separation effect during finish annealing.
• Table 4 shows the experimental results when the coating amount was changed. When the coating amount was extremely small, the annealing separation effect was insufficient and the steel sheet was seized. On the other hand, when the amount of coating increases, the adhesion of the annealing separator to the steel sheet decreases. From the above, it is preferable to control the application amount of the annealing separator in order to ensure good adhesion to the steel sheet and to have an annealing separation effect. Table 4
• the present invention By adopting the A1 compound as the main component and defining the solid content ratio and viscosity of the A1 compound, it is newly possible to obtain excellent coating properties and adhesion after coating. Heading, the present invention has been completed.
• the annealing separator of the present invention the method for annealing a grain-oriented electrical steel sheet, and the method for producing a grain-oriented electrical steel sheet will be described in detail. First, the reason for limiting the annealing separator will be described. Limitations are generally specified at the time of application to the steel sheet.
• A1 compound in the form of a solution or colloid solution as the main component of the annealing separator and a compound that is stable at high temperatures, that is, it has excellent high-temperature stability and does not react or hardly react during patch annealing.
• One or more compounds are used as the main components.
• the high-temperature stable compound may be in a solution state or a colloid solution state together with the A1 compound. That is, the annealing separator may be a solution or a colloid solution.
• being in a solution state means a state in which the compound is dissolved in water or an organic solvent as a medium.
• a colloid solution state means that particles of the compound having a size of about 100 nm or less are stably dispersed in the medium via a structural part such as a functional group having an affinity for the medium. Say state.
• the liquid serving as the medium is generically called a solvent.
• the colloid solution is similar to the solution because it is transparent without apparent suspension, but the presence of colloid particles is confirmed by light scattering measurements.
• the main component refers to a composition component other than the below-described auxiliary agent and additive.
• the main component accounts for about 65 mass% or more, preferably 75 ma SS % or more, based on the whole of the annealed separator component after drying (that is, the substance forming a solute or colloid).
• the liquid serving as the solvent and water or an organic solvent can be used.
• the organic solvent methanol, isopropanol, ethylene dalicol and the like are generally used, but not limited thereto.
• the use of water as a solvent is preferred from the viewpoint of cost and diversity of selection of the compound. This In this case, water may be mixed with an organic solvent of about 50 ma Ss % or less for the purpose of adjusting the liquid properties. In the above case where water is the main solvent, it is referred to as an aqueous annealing separator.
• the A1 compound and the compounds stable at high temperatures described above hardly react with the base iron unlike MgO used in conventional annealing separators, and thus significantly degrade punching workability such as forsterite coating. Does not form a coating. For this reason, it is very effective when supplying grain-oriented electrical steel sheets with excellent punching workability.
• the use of two or more compounds as the main components of the annealing separator is due to both the large annealing separation effect of a stable compound at high temperature and the good film-forming effect of a solution or colloidal A1 compound.
• the combination of the two functions effectively as an annealing separator for steel sheets with excellent applicability and adhesion to steel sheets after coating, and is particularly required for annealing separators for grain-oriented electrical steel sheets. Satisfies the characteristics.
• the A1 compound is limited to a compound that forms a colloid in a solvent such as water in order to secure a film forming function. That is, the A1 compound does not exhibit a film-forming effect unless it is in a colloidal state, so that adhesion cannot be obtained. For example, when alumina is applied as a slurry / suspension, no film is formed.
• the particle size of the A1 compound colloid is preferably about 50 mn or less. As for the lower limit, there is no suitable particle size limit, and the effect is sufficiently exhibited even near the analysis limit.
• the A1 compound is preferably an aluminum compound having a hydroxyl group and an organic acid group and / or a dehydration reaction product thereof (partially dehydration may be performed. The same applies hereinafter). More preferably, it is an aluminum compound comprising Al, a hydroxyl group and an organic acid group, and / or a dehydration product thereof.
• basic aluminum acetate, basic aluminum formate, basic aluminum hydrochloride, basic aluminum nitrate, basic aluminum oxalate, basic aluminum sulfamate, base Examples include one selected from basic aluminum lactate and basic aluminum citrate, or a mixture of two or more selected from these.
• basic aluminum acetate is represented by the molecular formula of Al x (0H) y (CH 3 C00) z , where x, y, and z are 1 or more, and in particular, Al 2 (OH) 5 (CH 3 COO) is preferred. It can exist from a dissolved state at the molecular level to a colloidal state of about several nm, and can be suitably used as a coating liquid material. Thermal analysis shows a large peak of the dehydration reaction at about 200 to 230 ° C, and heating forms a network between molecules by dehydration condensation to form a film. Part or all of the basic aluminum acetate and the like may have caused a dehydration reaction.
• the same A1 compound as that used in the case of the aqueous annealing separator can be used as a suitable A1 compound.
• High temperature stability as the compound except the M g 0, can be used known ones, is not particularly limited, for example, Si compounds, Sr compounds, Ca compounds, Zr compounds, Ti compounds, Ba compounds No. Specific compounds, Si0 2, SrO,
• Oxides such as TiO 2 , BaO, and CaO are mentioned.
• aqueous annealing separating agent for example, in the case of an aqueous annealing separating agent, it is necessary to use a chemical conversion to a form having a hydrophilic group such as a hydroxyl group. preferable.
• a state in which the surface is covered with a known hydrophilic substance in a solvent may be created.
• an organic solvent is used as a solvent, it may be designed based on a similar concept using a lipophilic group or the like.
• the high temperature when referring to a compound that is stable at high temperature refers to the annealing temperature, but for oriented magnetic steel sheets, 1200 ° C is sufficient if it is stable, and more preferably 1300 ° C. .
• the compound, it themselves, steel, or an oxide such as a steel sheet surface Si0 2, Fe0, Fe 3 0 4, Fe 2 Si0 4 , etc.
• All of the above compounds have the effect of improving the applicability of the annealing separator in coexistence with the A1 compound.
• Si compounds are particularly preferable from the viewpoint of applicability, annealing separation performance, and the like.
• colloidal silicon force As a Si compound, colloidal silicon force, The so-called colloidal silicide is particularly suitable because it has high stability with alumina sol and relatively low cost.
• Colloidal silica is an inorganic colloids which mainly components Si0 2, it is often amorphous.
• A1 compounds that are not a solution or colloid solution referred to as non-colloidal A1 compounds
• non-colloidal A1 compounds such as alumina particles
• the effect is small. Therefore, although the addition of the non-colloidal A1 compound itself as a part of the main component is not prohibited, it is preferable to include a compound which is stable at a high temperature other than the non-colloidal A1 compound.
• Non-colloidal A1 compounds shall not be considered in the calculation of the solid content ratio described below.
• the solid content ratio of the A1 compound is preferably 40 to 95 ma SS % in terms of the solid content ratio represented by the following formula (1).
• Solid content ratio of A1 compound (solid content of A1 compound) / ⁇ (solid content of A1 compound) + (solid content of high-temperature stable compound (sum)) ⁇ Formula (1)
• a silica sol silica i.e. Si0 2 is the main compound
• Wachi Ti0 2 such to titania is the main compound if titania sol.
• the baking step is not particularly provided, it is converted to the main compound generated when the baking treatment is performed.
• Solid content ratio of A1 compound (solid content of A1 compound) / (total solid content) Formula (3)
• solid content refers to the amount contained in the annealing separator after drying.
• the solid content ratio of the A1 compound is 40 mass ° /. If the ratio is less than the above, the amount of the A1 compound as a film forming component becomes insufficient, and the adhesion of the annealing separator becomes insufficient.
• the solid content ratio is 95 ma SS /. When the amount exceeds the limit, the amount of the highly reactive A1 compound becomes too large, Not determined. For this reason, a uniform film cannot be formed, and the appearance of the product becomes poor.
• Solid content of A1 compound is preferably, 50 mA SS%, more preferably, 60 mass%, more preferably at least 70 mass%. When at least one compound selected from the group of Si compound, Sr compound, compound, Zr compound, Ti compound and Ba compound is used as the compound stable at high temperature, the solid content of A1 compound is as follows. Replaced by equation (2).
• Solid content ratio of A1 compound (solid content of A1 compound) / ⁇ (solid content of A1 compound) + (the solid content of at least one compound (sum)) ⁇ formula (2)
• each compound is preferably a value converted to the weight of each compound described below.
• the viscosity in the present invention is a value obtained by measuring the viscosity of the annealing separator at the liquid temperature with an Ostwald viscometer.
• the amount of the S-containing compound to be added is about 25 ma SS ° / in solid content ratio to the annealing separator component after baking. It is preferable that: Even when the baking step is not particularly provided, the evaluation is made based on the solid content ratio of the S-containing compound generated when the baking treatment is performed.
• the S-containing compound is not particularly limited, but is preferably an inorganic S compound such as a sulfate (including a sulfite) and a metal sulfide. Specific examples include stotium sulfate, magnesium sulfate, and magnesium sulfide.
• Various methods such as a roll coater, a flow coater, a spray, and a knife coater, which are generally used in industry, can be applied as a method of applying the annealing separating agent. It is preferable that the annealing separator of the present invention be heated and baked after application.
• a method such as a hot air method, an infrared method, or an induction heating method, which is usually performed, can be applied.
• the conditions of the baking treatment may be set according to various circumstances, but usually, a preferable temperature is about 150 to 400 ° C and a preferable time is about 1 to 300 seconds.
• additives such as a surfactant and a heat-resistant agent may be blended.
• the content of the additive is preferably about iomass % or less based on the annealed separating agent component after drying in order to maintain a sufficient annealing separating effect as the annealing separating agent.
• Surfactants can be any of commercially available nonionic, anionic or cationic surfactants. These are also applicable.
• the type of the protective agent is not particularly limited, and a commercially available one can be used.
• the annealing separator of the present invention is particularly suitable for application to grain-oriented electrical steel sheets. The application to other steel sheets is not prohibited.
• the annealing separator of the present invention is particularly effective when the steel strip is heated in a furnace while being wound in a coil shape, but can also be applied to a case where a steel sheet is stacked and subjected to a heat treatment.
• preferred conditions for producing a grain-oriented electrical steel sheet according to the present invention will be described below.
• any composition known to be suitable for grain-oriented electrical steel sheets can be applied.
• the reasons for limiting the respective components of the preferred molten steel components in the typical component system will be described.
• the content of C exceeds 0.08 mass%, it is difficult to reduce C to 50 mass PP or less, at which magnetic aging does not occur, during the manufacturing process.Therefore, the content of C is set to 0.08 mass% or less. Is preferred. In particular, a lower limit is not required. Industrially, about 5 massppm is the limit of reduction.
• Si is an element effective in increasing the electrical resistance of steel and improving iron loss. To obtain the effect, it is preferable to contain 2.0 mass% or more. On the other hand, if it exceeds 8.0 mass%, the workability and the magnetic flux density decrease, so the upper limit is preferably set to 8.0 mass%. Therefore, a preferable Si content is 2.0 to 8.0 mass%. Mn: 0.005 to 1.0 mass%
• Mn is an element effective for improving hot workability, and is preferably added at 0.005 mass% or more. On the other hand, excess Mn lowers the magnetic flux density of the product plate. From this viewpoint, the preferable content of Mn is 1. Omass. /. It is as follows. Therefore, the preferable content of Mn is 0.005 to 1.0 mass. /. It is. In the production of grain-oriented electrical steel sheets, it is common to add an element that forms an inhibitor (inhibitor-forming component) in order to develop the Goss orientation during secondary recrystallization. However, it has recently become known that it is also possible to develop the Goss orientation without using inhibitors by reducing the impurity elements in steel.
• Sb and / or Sn are added to the grain-oriented electrical steel sheet in a total amount of about 0.005 to 0.1 mass%, since the magnetic properties can be further improved.
• slabs of normal dimensions may be manufactured by a normal ingot-making method or a continuous sintering method, or a thin slab piece of ioo mm or less (a so-called thin slab). May be directly manufactured by a manufacturing method. The slab is re-heated and hot-rolled by an ordinary method, but may be immediately hot-rolled without heating after fabrication.
• hot rolling may be performed, or hot rolling may be omitted and the process may proceed to the subsequent steps.
• the hot-rolled steel sheet is then subjected to annealing (hot-rolled sheet annealing) as necessary.
• annealing hot-rolled sheet annealing
• the hot-rolled sheet annealing temperature is preferably set to 800 ° C. or higher.
• the hot-rolled sheet annealing temperature is preferably 1100 ° C or less. Therefore, in order to highly develop the Goss structure in the product sheet, it is preferable that the hot-rolled sheet annealing temperature be 800 ° C or higher and 1100 ° C or lower.
• the preferred annealing time for hot-rolled sheet annealing is 1 to 300 seconds.
• recrystallization annealing is performed.
• intermediate annealing is interposed between each cold rolling.
• the intermediate annealing is preferably performed at 900 to 1200 ° C. for about 1 to 300 seconds.
• the cold rolling temperature may be increased by 100 to 250. This is treated as a type of cold rolling, called S, which is sometimes called warm rolling.
• S which is sometimes called warm rolling.
• the aging treatment in the range of 100 to 250 ° C may be performed once or plural times during the cold rolling.
• Recrystallization annealing is preferably performed by continuous annealing for the purpose of mainly forming a primary recrystallization structure.
• the recrystallization annealing may be performed in a dry atmosphere if decarburization is not required and the dehumidification is not required.
• Preferred recrystallization annealing conditions are 750 to 1100 ° C. for about 1 to 300 seconds. Adjusting the C content in the steel sheet to 100 to 250 massppm in the secondary recrystallization annealing (finish annealing or the first patch annealing when the final annealing is divided into two patch annealings) is particularly effective in containing inhibitors. This is suitable for improving the magnetic flux density in a non-oriented electrical steel sheet.
• the adjustment of the C content may be performed by recrystallization annealing or may be performed separately thereafter.
• the technique of increasing the amount of Si by the siliconizing method may be applied to, for example, a steel sheet after recrystallization annealing.
• the application of the annealing separator of the present invention is performed before or after recrystallization annealing.
• annealing separators have poor adhesion to steel sheets, so applying an annealing separator before recrystallization annealing was not possible from the viewpoint of line contamination due to peeling during recrystallization annealing.
• an annealing separator containing MgO as a main component which requires a long heating time to form a film.
• the annealing separator of the present invention has good adhesion to a steel sheet, and there is no fear of line contamination due to peeling, so that it can be applied before or after recrystallization annealing.
• the application amount of the annealing separator of the present invention is preferably 0.005 g / m 2 or more in order to exert the effect of preventing adhesion of the steel sheet.
• the amount of adhesion is preferably 5 g / m 2 or less. Therefore, it is preferable that the application amount of the annealing separator be in the range of 0.005 to 5 g / m 2 .
• a more preferred lower limit is 0.05 g / m 2 and a more preferred upper limit is 2 g / m 2 .
• the preferable application amount in the production of the grain-oriented electrical steel sheet is as described above. Depending on the heat treatment conditions and required quality of each force, it can be used outside the above-mentioned preferred range.
• the annealing separator may be applied to only one side or both sides of the steel sheet, but is preferably applied to both sides in order to surely obtain the effect. It is not prohibited to change the composition of the annealing separator on the front and back of the steel sheet, but it is preferable to apply the same annealing separator on both sides in the process.
• Magnetic properties without forsterite coating In the case of manufacturing a magnetic steel sheet, after the recrystallization annealing and the application of the annealing separator of the present invention, the finish annealing is performed by patch annealing. The purpose of finish annealing is to reduce (purify) impurities during the secondary recrystallization. Known annealing conditions can be applied as the annealing conditions.
• the preferred finish annealing temperature is about 750-1300 ° C, but the first half may be about 750-1000 ° C and the second half may be about 900-1300 ° C.
• secondary recrystallization is mainly promoted in the first half, and purification is mainly promoted in the second half.
• a preferable finish annealing time is about 1 to 300 hours as a holding time in the above temperature range.
• Methods for reducing C include a method of decarburizing during finish annealing and a method of adding a decarburization step after finish annealing.
• a method of decarburizing during finish annealing In order to decarburize during the finish annealing, it is recommended to perform high-temperature annealing at 1000 ° C or more during finish annealing, especially in the atmosphere containing hydrogen in the latter half.
• decarburization processes added after finish annealing include (1) annealing in an oxidizing atmosphere (decarburizing annealing), (2) surface grinding to mechanically remove surface graphite, and (3) surface grinding of Electrolytic cleaning to remove the graphite chemically, chemical polishing, plasma irradiation, etc. are effective.
• decarburization by means (2) or (3) is possible is that C precipitates as graphite on the surface of the steel sheet by the end of finish annealing, and decarburization in the steel has been completed. It is.
• C forms a metastable cementite in steel, S, and forms graphite in an activated state with high surface energy. Therefore, during cooling, C precipitates as graphite on the surface layer before it precipitates as cementite in the base iron.
• the solubility of graphite is slightly lower than that of cementite. Therefore, the concentration of solid solution C in the surface layer decreases to a concentration that is in equilibrium with the graphite, causing a concentration gradient between solid solution C in the surface layer and solid solution C in the ground iron, and decarbonization from the ground iron. It is speculated that this will progress.
• a dense or strong coating layer is formed on the surface during finish annealing (for example, when a conventional annealing separator containing MgO as a main component is applied), surface activation is hindered, and Precipitation of the steel sheet surface layer is also inhibited.
• the film formed by the annealing separator of the present invention is excellent in adhesion, it does not adversely affect the precipitation of the graphite steel sheet surface for any unknown reason, and the above decarburization method can be suitably used. .
• After finish annealing it is effective to correct the shape by applying tension by flattening annealing to reduce iron loss. By performing the flattening annealing in a humid atmosphere, decarburization may be performed at the same time (a type of the method (1)).
• a technique of increasing the amount of Si by the siliconizing method after the finish annealing may be further applied.
• This technology is effective for further reducing iron loss.
• an insulating coating to the surface of the steel sheet after flattening annealing.
• an organic coating containing a resin is desired as the insulating coating.
• weldability is important, it is desirable to apply an inorganic coating as an insulating coating.
• the first recrystallization after the recrystallization annealing and the application of the annealing separator of the present invention are required to develop secondary recrystallization.
• known annealing conditions under which secondary recrystallization proceeds can be applied. Preferred conditions are about 750 to 1100 ° C for about 1 to 300 hours.
• a forsterite coating is formed by the second patch annealing.
• a subscale is formed by continuous annealing.
• the first batch annealing is performed with a predetermined amount of C contained for the purpose of improving the magnetic properties, it is preferable that decarburization is simultaneously performed in the continuous annealing for forming the subscale.
• Known annealing conditions can be applied to the annealing conditions (time, temperature, atmosphere, etc.) of the continuous annealing so that the forsterite coating can be easily and stably formed in the subsequent batch annealing.
• the preferred annealing temperature is about 750 to 1000 ° C.
• the preferred annealing time is about 1 to 300 seconds
• the preferred atmosphere is an oxidizing atmosphere consisting of hydrogen gas and nitrogen gas.
• the step of removing the annealing separator of the present invention before the continuous annealing is unnecessary. That is, even if a forsterite coating is applied over the annealing separator of the present invention, not only the adhesion of the forsterite coating is good, but also the purification due to the presence of the annealing separator of the present invention. There is no hindrance.
• an annealing separator mainly composed of MgO is applied to the steel sheet surface, and a second batch annealing is performed. Since the second batch annealing is performed for the purpose of forming a forsterite coating and purifying impurities, known annealing conditions that can achieve the two purposes can be applied.
• the preferred annealing temperature is about 900-1300 ° C., and the preferred annealing time is about 1-300 hours.
• known annealing separators containing MgO as a main component can be used.
• the MgO about 8 0 to 99 mass%, the remainder optionally used Ti0 2, SRS0 4, MgSO be preferably those with one or more selected 4 and the like or al Can be
• the grain-oriented electrical steel sheet in the present invention means an electrical steel sheet in which secondary recrystallization has developed. Therefore, not only the Goss direction but also the Cube direction ( ⁇ 100 ⁇ The present invention also covers the case where (100) (011) orientation is secondary recrystallized.
• a known method can be applied to the accumulation in the Cube orientation, for example, it can be performed by controlling the rolling texture.However, the steps after recrystallization annealing are the same as the case where secondary recrystallization in which the Goss orientation is accumulated The same is true in the outline.
• a grain-oriented electrical steel sheet with excellent forsterite coating properties and magnetic properties was prepared by the following method.
• Oyopi Sb 380 comprises massppm, Al as a is et to Inhi Bitter forming component: 320 massppm
• Oyopi N A steel slab containing 80 massppm, the balance being iron and unavoidable impurities was produced by a continuous production method. After the steel slab was heated to 1200 ° C, it was hot-rolled to finish a hot-rolled sheet having a thickness of 2.0 mm, and annealed at 1050 ° C for 60 seconds.
• the annealing separator was applied before or after recrystallization annealing according to Table 5.
• the annealing separator was applied using a roll coater, and then subjected to a baking treatment at an ultimate temperature of the steel sheet (sheet temperature) of 250 ° C and allowed to cool.
• the baking was performed by propane gas baking.
• the first patch annealing was carried out in a nitrogen atmosphere at 850 ° C for 40 hours to complete the secondary recrystallization.
• a second patch annealing was performed in a dry hydrogen atmosphere at 1200 ° C for 5 hours.
• a tension coating was applied and baked and a strain relief annealing was performed.
• Tensile coatings containing phosphoric acid, coumic acid, and cinnamate were used and baked at a temperature of 800 ° C.
• the strain relief annealing was performed in a nitrogen atmosphere at 800 ° C for 3 hours.
• Table 5 shows the components of the annealing separator and the application conditions. S i0 2, the annealing separator composed A1 2 0 3 powder the main components was applied by the exception water slurry scratch No. 26, No. 26 is to be a solid 5 mas s% in alcohol And applied by spraying.
• the ratio of the main component other than powder was different depending on the amount of application, but was diluted with water and applied as a colloid solution. 3 wt% each of sodium sulfate, magnesium sulfate and magnesium sulfide added as adjuncts. /. Added. Solid contents other than those described in Table 5 were not added, but a surfactant (non-ion type) or the like was appropriately added at 0.5 mass% or less.
• Table 6 shows the order of the annealing separator application process (before or after recrystallization annealing), the coating properties of the annealing separator, and the annealing separator after drying. 5 shows the adhesion and the effect of annealing separation after the first patch annealing.
• Nos. 1 to 4 had insufficient adhesion to the steel sheet because the main component of the annealing separator was outside the present invention.
• adhesion of the steel sheet occurred at the time of finish annealing because the amount of the applied annealing separator was insufficient.
• No. 17 had too much applied amount of annealing separator Therefore, peeling occurred due to insufficient adhesion to the steel sheet.
• the annealing separator was applied in two different order, before and after recrystallization annealing. Regardless of the sequence of the annealing separator application step, the annealing separator of the present invention has good applicability of the annealing separator, adhesion of the annealing separator after drying, and annealing separation effect after the first batch annealing. Obtained. In Comparative Examples Nos. 3, 4, and 26, the annealing separation effect was different depending on the application sequence of the annealing separating agent.
• Table 7 shows the magnetic properties, forsterite coating properties, and 1, (, 3) after the second batch annealing when the sample to which the annealing separator of the present invention was applied was subjected to subsequent steps to obtain a product plate.
• 36 content (results of analysis after removing the coating in the base steel, that is, the surface of the steel sheet)
• Forsterite coating characteristics are as follows: the sample after strain relief annealing was wound around a cylinder to remove the coating. was evaluated by the minimum bend radius not occurred.
• B 8 is magnetic flux density at a magnetizing force 800A / m (T)
• W 17 / 50 is the iron loss value (W / kg) at a frequency of 50 Hz and a maximum magnetic flux density of 1.7 T.
• a grain-oriented electrical steel sheet having excellent forsterite coating properties and magnetic properties was prepared by the following method.
• the first patch annealing was performed.
• Table 8 shows the annealing separators. Accordingly, it was applied before or after recrystallization annealing.
• Application of annealing separator was performed using a roll coater primary, then baked at the ultimate temperature 2 50 ° C, and allowed to cool. Baking was carried out by baking with propane.
• the first patch annealing was performed in a nitrogen atmosphere at 865 ° C. for 50 hours to complete the secondary recrystallization.
• annealing separator After that, the applicability of the annealing separator, the adhesion of the annealing separator after drying, and the annealing separation effect after the first patch annealing were investigated, and for samples with good results, the subsequent steps were further performed. , And product plate. 'In a subsequent step, first, they performed continuously annealed to form a good subscale, then coated with an annealing separator composed mainly of M g 0. Since the first batch annealing was performed with 100 to 150 mass ppm of C remaining, decarburization was performed simultaneously in the continuous annealing performed to form this subscale. The continuous annealing was performed at 850 ° C for 80 seconds in an oxidizing atmosphere with a dew point of 60 ° C.
• annealing separator Mg0 as solid content: 92. 5 mas s%, Ti0 2: 7. 5 mas s. /. Used was used.
• a second batch annealing was performed.
• the temperature was kept at 1100 ° C, which is lower than before, for 5 hours, and the atmosphere was changed to hydrogen.
• a tension coating was applied and baked and a strain relief annealing was performed.
• Tensile coatings containing phosphoric acid and oxalic acid were used and baked at 800 ° C.
• the strain relief annealing was performed in a nitrogen atmosphere at 800 for 3 hours.
• the components of the annealing separator and the application conditions were the same as in Example 1 under the conditions corresponding to each No. shown in Table 5.
• Table 8 shows the order of the separating agent application process (before or after recrystallization annealing), the applicability of the annealing separating agent, the adhesion of the annealing separating agent after drying, and the annealing separation effect after the first patch annealing.
• Example 1 for the steel produced by the method of the present invention, regardless of the sequence of the step of applying the annealing separator, good coatability of the annealing separator, adhesion of the annealing separator after drying, Separation effect after first and first patch annealing Is obtained. This shows that the annealing separator of the present invention is effective even when applied to a component system containing no inhibitor.
• Table 9 shows the magnetic properties, forsterite coating properties, and the Al, C, N, and B values after the second batch annealing when the sample to which the annealing separator of the present invention was applied was subjected to subsequent steps to obtain a product plate. Shows the S and Se contents. The method of investigating each characteristic was the same as in Example 1.
• a grain-oriented electrical steel sheet having no forsterite coating and excellent magnetic properties and workability was prepared by the following method.
• cold rolling was performed to form a cold rolled sheet with a thickness of 0.27 mm
• recrystallization annealing was performed at 880 ° C for 10 s in a dry atmosphere with a dew point of -45 ° C, and then finish annealing was performed. .
• the annealing separator was applied before or after recrystallization annealing according to Table 10. Coating was carried out using a roll coater, and was baked at an ultimate plate temperature of 250 ° C and then allowed to cool. The baking was done by baking bread over open fire. 45 at 860 ° C for finish annealing After secondary recrystallization by holding in an N 2 atmosphere for a period of time, purification was performed by holding in an H 2 atmosphere at 1200 ° C. for 5 hours. As in Example 1, the components of the annealing separator and the application conditions were set under the conditions corresponding to each No. shown in Table 5.
• the insulating coating used was a cuprate-based one containing a commonly used organic resin, and was baked at a temperature of 300 ° C.
• the strain relief annealing was performed in a nitrogen atmosphere at 750 ° C for 2 hours.
• Table 10 shows the applicability of the annealing separator, the adhesion of the annealing separator after drying, the annealing separation effect after finish annealing, the magnetic properties, the properties of the insulating coating, and the 1,2,3,36 content after finish annealing. Is shown. In Nos.
• the order of applying the annealing separator was two before and after recrystallization annealing.
• the annealing separator of the present invention has good coating properties of the separating agent, adhesion of the separating agent after drying, and finish annealing regardless of the sequence of the annealing separating agent application step. An annealing separation effect at the time is obtained.
• Comparative Examples Nos. 1 and 4 there was a difference in the annealing separation effect depending on the application sequence of the annealing separating agent. This is considered to be due to the difference in the amount of the annealing separator attached during the final annealing for the same reason as in Example 1.
• the one to which the annealing separator according to the present invention is applied has good applicability of the annealing separator, adhesion of the annealing separator after drying, annealing separation effect after finish annealing, magnetic properties, insulation coating properties, and impurities in the base iron. It can be seen that this indicates the purification of In particular, the film properties were better than those of the forsterite films shown in Examples 1 and 2. This shows that the annealing separator of the present invention can be advantageously applied to a grain-oriented electrical steel sheet that uses an inhibitor and requires purification by high-temperature annealing.
• a grain-oriented electrical steel sheet having no forsterite coating and excellent in magnetic properties and workability was prepared by the following method.
• Oyopi Se A steel slab containing no inhibitor-forming component, each of which was suppressed to less than 10 massppm, was produced by a continuous casting method. The balance was iron and inevitable impurities. After the steel slab was heated to 1200, it was hot-rolled into a hot-rolled sheet having a thickness of 1.8 mm, and annealed at 950 ° C for 6.0 seconds.
• the annealing separator was applied before or after recrystallization annealing according to Table 11.
• the coating was performed using a mouth coater, and was baked at an ultimate plate temperature of 250 ° C and then allowed to cool. The baking was performed by baking bread directly on the fire.
• finish annealing is secondary recrystallization by holding at 87 5 ° C with 45 hours between the N 2 atmosphere and maintained at subsequent 1000 ° C in a 5:00 between Ar atmosphere.
• decarburization annealing was performed in an oxidizing atmosphere to reduce the amount of C in the base steel.
• the components of the annealing separator and the application conditions were set under the conditions corresponding to each No. shown in Table 5.
• the insulating film used was a chromate-based material containing a commonly used organic resin, and was baked at a temperature of 300 ° C.
• the strain relief annealing was performed in a nitrogen atmosphere at 750 ° C for 2 hours.
• Table 11 shows the applicability of the annealing separator, the adhesion of the annealing separator after drying, the annealing separation effect after finish annealing, the magnetic properties, the insulating coating properties, and the Al, C, N, S, and Se after finish annealing. Shows the content.
• good results were obtained with steel to which the annealing separator according to the present invention was applied irrespective of the sequence of the annealing separator applying step.
• a grain-oriented electrical steel sheet was prepared by applying the annealing separator shown in Table 12.
• the manufacturing process is as shown in Table 13.
• Steps A and B (the method using the final annealing) were performed in Example 3, and Steps C and D (the method using the two patch annealings) were performed according to Example 1.
• Slab and manufacturing conditions were applied.
• the annealing separator the components other than the main components and the application conditions were the same as in Example 1. No. 6 was substantially recognized as a solution because no light scattering was recognized by the light scattering method.
• Viscosity Solid content ratio (mass ⁇ 1 ⁇ 2)
• Each steel slab having the components described in Table 14 was 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 according to the classification in Table 15.
• the C content before secondary recrystallization was not particularly adjusted, and therefore the decarburization treatment was omitted.
• recrystallization annealing was performed in an oxidizing atmosphere with a dew point of 30 ° C, and the C content before secondary recrystallization annealing was adjusted to 100 to 150 mass ppm.
• the conditions for applying the annealing separator were in accordance with No. 13 in Table 5.
• Table 15 shows the results. The magnetic properties also depend on the composition of the steel sheet, but all achieve the expected magnetic properties for each component. Table 14
• the annealing separator for grain-oriented electrical steel sheets according to the present invention has good coatability and adhesion to a steel sheet, and can secure a stable operation in the step of applying the annealing separator and the subsequent steps. It also has excellent operability, such as achieving adhesion, without impeding purification and decarburization, and eliminating the need for coating removal work.

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