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    • 专利摘要:
    patent summary: "method for producing grain oriented electric steel sheet". In this method to produce a oriented electromagnetic steel plate, a steel plate containing by weight% 0.001 to 0.10% c, 1.0 to 5.0% of itself, 0.01 to 1 is subjected. , 0% min, a total of 0.01 to 0.05% se and, 0.003 to 0.050% sol, and 0.001 to 0.020% hot rolling, cold rolling, primary recrystallization annealing, Coating with an annealing separation agent having mgo as the main component, and finishing annealing, the heating rate (s1) between 500 and 600 ° C in the primary recrystallization annealing is at least 100 ° c / s, the heating rate (s2) between 600 and 700ºc is 30ºc / s 0.6xs1oc / s, the ionic rays contained in the annealing separation agent are 0.6 to 1.3 å, and the total amount contained (w) (mol%) with respect to The range of elements having an oxygen ion attraction of not more than 0.7 å-2 is adjusted to satisfy 0.01s2 to 5.5 = ln (w) = 0.01s2 - 4.3.
    公开号:BR112014002666B1
    申请号:R112014002666-1
    申请日:2012-08-15
    公开日:2018-11-06
    发明作者:Makoto Watanabe；Yukihiro Shingaki；Toshito Takamiya；Tomoyuki Okubo；Kunihiro Senda
    申请人:Jfe Steel Corporation；
    IPC主号:
    专利说明:

    (54) Title: METHOD TO PRODUCE GUIDED GRAIN ELECTRIC STEEL SHEET (51) IntCI .: C21D 8/12; C22C 38/00; C22C 38/60; C23C 22/00; H01F 1/16.
    (30) Unionist Priority: 08/18/2011 JP 2011-178841; 07/20/2012 JP 2012-161139.
    (73) Holder (s): JFE STEEL CORPORATION.
    (72) Inventor (s): MAKOTO WATANABE; YUKIHIRO SHINGAKI; TOSHITO TAKAMIYA; TOMOYUKI OKUBO; KUNIHIRO SENDA.
    (86) PCT Application: PCT JP2012070758 of 08/15/2012 (87) PCT Publication: WO 2013/024874 of 02/21/2013 (85) Date of the Beginning of the National Phase: 04/02/2014 (57) Summary: ABSTRACT Patent of Invention: METHOD TO PRODUCE GUIDED GRAIN ELECTRIC STEEL SHEET. In this method to produce a oriented electromagnetic steel sheet, a steel sheet containing 0.001 to 0.10% C, 1.0 to 5.0% Si, 0.01 to 1 is submitted , 0% Mn, a total of 0.01 to 0.05% S and Se, 0.003 to 0.050% Al sol., And 0.001 to 0.020% N N hot rolling, cold rolling, recrystallization annealing primary, coating with an annealing separating agent having MgO as the main component, and finishing annealing, the heating speed (Sl) between 500 and 600 ° C in the primary recrystallization annealing is at least 100 ° C / s, at heating speed (S2) between 600 and 700 ° C is 30 ° C / s to 0.6xSloC / s, the ionic rays contained in the annealing separation agent are 0.6 to 1.3 Å, and the total amount contained ( W) (mol%) with respect to MgO of elements having an oxygen ions attraction of not more than 0.7 Â-2 is adjusted to satisfy 0.01S2 to 5.5 = Ln (W) = 0.01S2 - 4.3.
    1/35
    Descriptive Report of the Invention Patent for METHOD TO PRODUCE GUIDED GRAIN ELECTRIC STEEL SHEET.
    Field of the Invention [001] The present invention relates to a method for producing a grain-oriented electric steel sheet, and more particularly a method for producing a grain-oriented electric steel sheet having excellent magnetic loss properties and properties coating over the entire length of a product coil. Here, the coating means a ceramic coating composed mainly of forsterite (Mg2SiO4) (hereinafter simply called coating), and the coating properties signify the appearance qualities of the coating such as the presence or absence of color irregularity, dots or similar coating.
    Background of the Invention [002] Electric steel sheets are soft magnetic materials widely used as core materials for transformers, power generators, or the like. Especially, grain-oriented electric steel sheets have good magnetic loss properties leading directly to the reduction of energy loss in transformers, power generators or the like, because their crystal orientation is highly concentrated in {110} <001> orientation, called the Goss orientation. In order to improve the magnetic loss properties, it is known that the reduction of the plate thickness, the increase of the specific electrical resistance by the addition of Si or similar, the improvement of the orientation in the crystal orientation, the application of tension to the plate steel, the softening of the steel sheet surface, the refinement of secondary recrystallized grains, the refinement in the magnetic domain and so on are effective.
    Petition 870180068354, of 08/07/2018, p. 5/45
    2/35 [003] Among them, a method of rapid heating during decarburizing annealing or a method where a primary recrystallization texture is enhanced by rapid heating just before decarburizing annealing is known as the technique for refining secondary recrystallized grains . For example, Patent Document 1 describes a technique of obtaining an electrical grain-oriented steel sheet with a low magnetic loss by rapid heating to a laminated steel sheet to a final thickness of 800 to 950 ° C and a heating rate of not less than 100 ° C / s in an atmosphere having an oxygen concentration of not more than 500 ppm before decarburizing annealing, and undergoing decarburization annealing under conditions that a preceding zone temperature in decarburizing annealing is 775 to 840 ° C lower than the temperature reached by rapid heating and a temperature of the subsequent zone is 815 to 875 ° C higher than the temperature of the preceding zone, and Patent Document 2 describes a technique of obtaining a plate oriented grain electric steel with a low magnetic loss by heating a rolled steel sheet to a final thickness to a temperature of not more than 700 ° C at a heating rate of no less than 100 ° C / s in a non-oxidizing atmosphere having a PH2O / PH2 of not more than 0.2 just before the decarburization annealing.
    [004] Also, Patent Document 3 describes a technique of producing an electric steel sheet having excellent coating and magnetic properties where a temperature zone of not less than 600 ° C in a one-step temperature rise stage decarburization annealing temperature is heated above 800 ° C at a temperature rise rate of not less than 95 ° C / s and an atmosphere of that temperature zone is constituted
    Petition 870180068354, of 08/07/2018, p. 6/45
    3/35 flow with an inert gas containing 10 ' 6 ~ 10' 1 oxygen as a fraction of volume, and an atmosphere in a decarburization annealing remedy is H2 and H2O or H2, H2O and an inert gas as a constituent and has a PH2O / PH2 of 0.05 to 0.75 and a flow rate per unit area of 0.01 to 1 Nm 3 / min · m 2 , and an angle of deviation from a crystal orientation of crystal grains of the steel sheet in a mixed region between the coating and the steel sheet is controlled to a suitable range of Goss orientation, and Patent Document 4 describes a technique of producing a grain-oriented electric steel sheet having excellent properties of coating and magnetic properties, where a temperature zone of not less than 650 ° C in a temperature rise stage of a decarburization annealing step is heated above 800 ° C at a temperature rise rate of not less than 100 ° C / s and an atmosphere of that temperature zone is an inert gas containing 10 ' 6 ~ 10' 2 oxygen as a volume fraction, while an atmosphere in a decarburization annealing remedy is H2 and H 2 O or H 2 and H 2 O and an inert gas as a constituent, and has PH2O / PH2 from 0.15 to 0.65, where a discharge time indicating a peak emission intensity Al in GDS analysis of a coating and a discharge time indicating that the intensity of Fe emission is% of a bulk value are controlled to suitable ranges.
    Prior Art Documents Patent Documents [005] Patent Document 1: JP-A-H10-298653 [006] Patent Document 2: JP-A-H07-062436 [007] Patent Document 3: JP-A-2003 -27194 [008] Patent Document 4: Japanese Patent No. 3537339
    Summary of the Invention
    Petition 870180068354, of 08/07/2018, p. 7/45
    4/35
    Problem to be solved by the invention [009] By applying these techniques, the secondary recrystallized grains are refined and the coating properties are improved, but there is a difficult situation to be perfect. For example, the Patent Document 1 technique conducts a temperature maintenance treatment at a temperature lower than the range temperature, since the temperature is raised to a certain higher temperature, but the range temperature is often outside of a target temperature because it is difficult to control. As a result, there is a problem that the variation in quality on the same coil or coil by coil is wide and lacks stability. In the technique of Patent Document 2, PH2O / PH2 of the atmosphere at temperature rise is reduced to no more than 0.2, but the improvement of the coating properties cannot be said to be sufficient, because not only the PH2O partial pressure ratio / PH2 of H2O and H2, but also the absolute partial pressure of H2O ultimately exert the coating properties as described in Patent Document 4, so that there is still room for further improvement.
    [0010] In the technique of Patent Document 3, there is a characteristic that the orientation of the crystal grains of the mixed region between the coating and the base metal is displaced from the orientation of Goss, but this characteristic can lead to the deterioration of the magnetic properties when the harmonic components are superimposed due to the complicated magnetization procedure configured in a transformer even though the magnetic properties in a test piece of cut sheet along the length are improved. In the technique of Patent Document 4, the temperature is raised at the same partial pressure of oxygen as in Patent Document 3, so there is a problem where the orientation of the
    Petition 870180068354, of 08/07/2018, p. 8/45
    5/35 crystal grains in the mixed region between the coating and the base metal are shifted from the Goss orientation as in Patent Document 3. Furthermore, there is a problem in which the Al peak position in GDS is altered by delicate variation in the chemical composition of steel or production conditions in the cold rolling stage and becomes unstable. That is, the peak position of Al can be shifted towards the surface of the steel sheet by delicate variation of ingredient such as Al, C, Si, Mn and the like, or by temperature, atmosphere or similar profile in the annealing of a hot-rolled sheet, which causes a problem that the magnetic properties or coating properties become unstable.
    [0011] The invention is made in view of the problems above conventional techniques, and proposes an advantageous production method of grain-oriented electric steel sheets that provides low magnetic loss properties over the entire length of a product coil by refinement of secondary recrystallized grains and can form a uniform coating.
    Solution to the problem [0012] In order to solve the above problems, the inventors focused on the temperature rise process in the annealing of primary recrystallization and secondary ingredients were added to an annealing separator and have the research conditions required to refine the secondary recrystallized grains stably and ensure the uniformity of a coating. As a result, it was concluded that it is effective to divide the heating process of the primary recrystallization annealing into a low temperature zone and a high temperature zone and to separately control the rate of temperature rise in each temperature zone for a range proper. That is, it was concluded that the secondary recrystallized grains are refined by increasing the rate of temperature rise in the
    Petition 870180068354, of 08/07/2018, p. 9/45
    6/35 annealing of primary recrystallization, but the inventors examined further and found that the rate of temperature rise in a recovery process as a preliminary process of primary recrystallization is made higher than a rate of temperature rise in decarburization annealing usual, while the rate of temperature rise in a high temperature zone causing primary recrystallization is restricted to no more than 60% of the rate of temperature rise in the low temperature zone, where the bad influence by the variation of production conditions can avoided to stably provide the effect of reducing magnetic loss. Furthermore, it was concluded that a uniform coating can be stably formed by adjusting an amount of secondary ingredient added to an annealing separator with a suitable range in response to the rate of temperature rise in the high temperature zone, and the invention was carried out .
    [0013] The invention is based on the above knowledge is a method for producing an electric grain steel plate oriented by hot rolling a steel plate of a chemical composition comprising C: 0.001 to 0.10% by weight, Si: 1.0 to 5.0% by weight, Mn: 0.01 to 1.0% by weight, at least one of S and Se: 0.01 to 0.05% by weight in total, Al sol .: 0.003 at 0.050% by weight, N: 0.001 at 0.020% by weight and the balance being Fe and unavoidable impurities, undergoing a single cold rolling or two or more cold rolling including an intermediate annealing between them to a final thickness and further to a primary recrystallization annealing, application of an annealing separator composed mainly of MgO and a finishing annealing, characterized by the fact that in the primary recrystallization annealing, a temperature rise rate S1 between 500 and 600 ° C is no less than 100 ° C / s, and a temperature rise rate S2 between 600 and
    Petition 870180068354, of 08/07/2018, p. 10/45
    7/35
    700 ° C is made 30 ° C / s 0.6 x S1 ° C / s, while the total content W (% in mol) of an element having an ionic radius of 0.6 to 1.3 Â and a strength of attraction between ion and oxygen of not more than 0.7 Å -2 included in the annealing separator the MgO is adjusted to satisfy the following equation (1) in relation to S2:
    0.01 S2 - 5.5 <Ln (W) <0.01 S2 - 4.3 (1) [0014] The method of producing the grain-oriented electric steel sheet according to the invention is characterized by the fact that that decarburization annealing is performed after primary recrystallization annealing.
    [0015] Also, the production method of the grain electric steel sheet oriented according to the invention is characterized by the fact that the element having an ionic radius of 0.6 to 1.3 Â and a force of attraction between the ion and oxygen of not more than 0.7 Â -2 is at least one among Ca, Sr, Li and Na.
    [0016] In addition, the production method of the grain electric steel sheet oriented according to the invention is characterized by the fact that in addition to the above chemical composition, the steel sheet contains at least one selected from Cu: 0.01 to 0.2% by mass, Ni: 0.01 to 0.5% by mass, Cr: 0.01 to 0.5% by mass, Sb: 0.01 to 0.1% by mass, Sn: 0 , 01 to 0.5% by mass, Mo: 0.01 to 0.5% by mass and Bi: 0.001 to 0.1% by mass.
    [0017] Furthermore, the production method of the grain electric steel sheet oriented according to the invention is characterized by the fact that in addition to the above chemical composition, the steel sheet contains at least one selected from B: 0.001 at 0.01% by mass, Ge: 0.001 at 0.1% by mass, As: 0.005 at 0.1% by mass, P: 0.005 at 0.1% by mass, Te: 0.005 at 0.1% by mass mass, Nb: 0.005 to 0.1% by mass, Ti: 0.005 to 0.1% by mass, and V: 0.005 to 0.1% by mass. Effect of the Invention
    Petition 870180068354, of 08/07/2018, p. 11/45
    [0018] According to the invention, the secondary recrystallized grains can be refined along the entire length of a coil of electric grain steel sheet product oriented to reduce magnetic loss, and even the uniform coating can be formed along the total length of the coil, so that the yield of the product can be greatly improved. In addition, the magnetic loss properties of a transformer or the like can be greatly enhanced using an electrical grain-oriented steel plate produced by the method of the invention.
    Embodiments for Carrying Out the Invention [0019] First, the chemical composition of the steel plate as a raw material of the electric grain steel sheet oriented according to the invention will be described.
    [0020] C: 0.001 to 0.10% by weight [0021] C is a useful element to generate Goss orientation grains and it needs to be included in an amount of not less than 0.001% by mass in order to develop such It is made. While, when C exceeds 0.10% by mass, it is difficult to decarburize to no more than 0.005% by mass in subsequent decarburization annealing to avoid causing magnetic aging. So, C is in the range of 0.001 to 0.10% by mass. Preferably, it is in the range of 0.01 to 0.08% by mass.
    [0022] Si: 1.0 to 5.0% by mass [0023] Si is an element required to increase the electrical resistance of steel to reduce magnetic loss and stabilize the BCC structure of iron to conduct heat treatment at a temperature higher, and it needs to be added in an amount of at least 1.0% by mass. However, the addition exceeding 5.0% by mass hardens the steel and it is difficult to conduct cold rolling. So, Si is in the range of 1.0 to 5.0% by mass. Preferably,
    Petition 870180068354, of 08/07/2018, p. 12/45
    9/35 it is in the 2.5 to 4.0% mass range.
    [0024] Mn: 0.01 to 1.0% by mass [0025] Mn contributes effectively to improve the hot brittleness of steel and is also an element that forms precipitates of MnS, MnSe or similar to develop an inhibitor function when S and Se are included. When the Mn content is less than 0.01 wt%, the above effects are not sufficiently achieved, while when it exceeds 1.0 wt%, precipitates such as MnSe and the like are thickened to lose the inhibitory effect . So, Mn is in the range of 0.01 to 1.0% by mass. Preferably, it is in the range of 0.04 to 0.40% by mass.
    [0026] Al sol .: 0.003 to 0.050% by weight [0027] Al is a useful element that forms AIN in steel, which precipitates as a second dispersion phase and acts as an inhibitor. However, when the amount of addition is less than 0.003% by mass as Al sol., The amount of precipitated AIN is insufficient, while when it exceeds 0.050% by mass, AIN is coarsely precipitated to lose the inhibitor action. So, Al is in the range of 0.003 to 0.050% by mass as Al sol. Preferably, it is in the range of 0.01 to 0.04% by mass.
    [0028] N: 0.001 to 0.020% by mass [0029] N is an element required to form AIN, like Al. However, when the amount of addition is less than 0.001% by mass, the precipitation of AIN is insufficient, while when it exceeds 0.020% by mass, bubbles or the like are caused by heating the plate. So, N is in the range of 0.001 to 0.020% by mass. Preferably, it is in the range of 0.005 to 0.010% by mass. [0030] At least one of S and Se: 0.01 to 0.05% by weight in total.
    [0031] S and If are useful elements that develop the action as
    Petition 870180068354, of 08/07/2018, p. 13/45
    10/35 an inhibitor that forms MnSe, MnS, Cu 2x Se or Cu 2x S through binding with Mn or Cu and precipitating into steel as a second dispersion phase. When the total amount of S and Se is less than 0.01% by mass, the above effect is not sufficiently achieved, whereas when it exceeds 0.05% by mass, not only is the solution insufficient to heat the plate, but it also causes surface defects on a product plate. So, S and Se are in the range of 0.01 to 0.05% by weight in any of the single addition and the compound addition. Preferably, they are in the range of 0.01 to 0.03 mass% in total.
    [0032] In addition to the above necessary ingredients, the steel plate on the electrical grain oriented steel plate of the invention can contain at least one selected from Cu: 0.01 to 0.2% by weight, Ni: 0, 01 to 0.5% by mass, Cr: 0.01 to 0.5% by mass, Sb: 0.01 to 0.1% by mass, Sn: 0.01 to 0.5% by mass, Mo: 0.01 to 0.5% by mass and Bi: 0.001 to 0.1% by mass.
    [0033] Cu, Ni, Cr, Sb, Sn, Mo and Bi are elements that segregate easily on the threshold or surface of the crystal grain and are also elements that have a subsidiary action as an inhibitor, so that they can be added with the purpose of further improving the magnetic properties. However, when the amount of addition of any element is less than the lower limit above, the effect of suppressing the thickening of the primary recrystallized grains in a higher temperature zone of the secondary recrystallization process is insufficient, while when the amount of addition exceeds the upper limit above, there is a fear of causing poor coating appearance or poor secondary recrystallization. So, if they are added, it is preferable to add them in the range mentioned above.
    [0034] In addition to the necessary ingredients above and the addition
    Petition 870180068354, of 08/07/2018, p. 14/45
    11/35 of arbitrary ingredients, the steel plate on the electrical grain oriented steel plate of the invention can contain at least one selected from B: 0.001 to 0.01% by weight, Ge: 0.001 to 0.1% in mass, As: 0.005 to 0.1% by mass, P: 0.005 to 0.1% by mass, Te: 0.005 to 0.1% by mass, Nb: 0.005 to 0.1% by mass, Ti: 0.005 to 0.1% by mass and V: 0.005 to 0.1% by mass.
    [0035] B, Ge, As, P, Te, Nb, Ti and V also have a subsidiary action as an inhibitor and are effective elements to further improve the magnetic properties. However, when they are less than the amount of addition above, the effect of suppressing the thickening of the primary recrystallized grains in a higher temperature zone of the secondary recrystallization process is insufficient, whereas when the addition exceeds the upper limit above, there is a fear of causing poor secondary recrystallization or poor appearance of the coating. So, if they are added, it is preferable to add them in the range mentioned above.
    [0036] Next, the method of producing the electric grain steel sheet oriented according to the invention will be described.
    [0037] The electrical grain-oriented steel sheet of the invention is produced by a method comprising a series of steps of melting steel having the chemical composition mentioned above by a conventionally well-known refinement process, forming a crude steel material (plate steel) by a method such as continuous casting method, ingot-rolling method or similar, hot-rolling the steel plate to form a hot-rolled sheet, subjecting the hot-rolled sheet to an annealing if necessary, subject to a single cold rolling or two or more cold rolling including intermediate annealing to form a cold rolled sheet of a final thickness, subjecting the cold rolled sheet to a recrystallization annealing
    Petition 870180068354, of 08/07/2018, p. 15/45
    12/35 priming and decarburizing annealing, apply an annealing separator composed mainly of MgO, subject to a final finish annealing and then subject to planing annealing combined with the application / firing of an insulation coating, if necessary .
    [0038] In this production method, production conditions, other than primary recrystallization annealing and annealing separator, are not particularly limited because conventionally well-known methods can be adopted. Then, the primary recrystallization annealing conditions and conditions in the annealing separator will be described below.
    Primary recrystallization annealing [0039] The condition of subjecting the cold rolled sheet of the final thickness to primary recrystallization annealing, particularly the rate of temperature rise in the heating process has a major influence on the secondary recrystallization structure as previously mentioned, so it is required to severely control the rate of temperature rise. In the invention, then, the heating process is divided into a low temperature zone following recovery and a high temperature zone causing primary recrystallization and the rate of temperature rise in each zone is appropriately controlled so that the secondary recrystallized grains they are stably refined over the entire length of the product spool to improve the ratio of a part with excellent magnetic loss properties of the product spool.
    [0040] Concretely, the rate of temperature rise S1 of the low temperature zone (500 to 600 ° C) causing recovery as a precursor to primary recrystallization is made no less than 100 ° C / s higher than the usual case, while the rate
    Petition 870180068354, of 08/07/2018, p. 16/45
    13/35 rise in temperature S2 of the high temperature zone (600 to 700 ° C) causing primary recrystallization is done not less than 30 ° C / s and no more than 60% of the rate of temperature rise of the zone low temperature. Thus, even if the chemical composition of the steel or the production conditions prior to primary recrystallization annealing are varied, the secondary recrystallized grains can be refined to provide low magnetic loss along the entire length of the product coil.
    [0041] Explaining this reason, it is known that the secondary recrystallization core of Goss orientation {110} <001> exists in a deformation band caused by fiber texture <111> responsible for storing deformation energy in a laminated texture. The deformation band is a region that particularly stores deformation energy in the fiber texture <111>.
    [0042] When the rate of temperature rise S1 in the low temperature zone (500 to 600 ° C) as the process of heating the primary recrystallization annealing is less than 100 ° C / s, the recovery (decrease of the energy of deformation) is preferably caused in the deformation band having a very high deformation energy, so that the orientation recrystallization from Goss {110} <001> cannot be promoted. In contrast, when S1 is made not less than 100 ° C / s, the deformation structure can be maintained up to a higher temperature in a state of high deformation energy, so that the orientation recrystallization from Goss {110} <001> can be caused at a relatively low temperature (approximately 600 ° C). That is the reason for making S1 not less than 100 ° C / s. Preferably, S1 is not less than 120 ° C / s.
    [0043] On the other hand, in order to control the size of the recrystallized secondary grains of orientation of Goss {110} <001>, it is im
    Petition 870180068354, of 08/07/2018, p. 17/45
    14/35 therefore controlling an amount of structure <111> invaded by the orientation of Goss {110} <001> for an appropriate range. That is, when the <111> orientation is very large, the growth of the secondary recrystallized grains is promoted and there is a fear that even if there are many orientation cores of Goss {110} <001>, a structure is thickened to form grains thick before the growth of these kernels, while when the <111> orientation is very small, secondary recrystallized grains are difficult to grow and there is a fear of causing secondary recrystallization failure.
    [0044] As the <111> orientation is caused by recrystallization from the fiber texture <111> having greater deformation energy than that of the surroundings although it does not have as much deformation energy as the deformation band, it is a crystal orientation easily causing recrystallization close to the Goss orientation {110} <001> in the heating cycle of the invention, where heating is carried out at the rate of temperature rise S1 to 600 ° C of not less than 100 ° C / s . So when heating is carried out at a high temperature rise rate to such a high temperature that crystal grains other than Goss 'orientation cause primary recrystallization (not less than 700 ° C), Goss' orientation {110} <001> and the subsequently recrystallizable <111> orientation reach high temperature in a suppressed recrystallization state and then all orientations cause recrystallization immediately. As a result, the texture after primary recrystallization is randomized to decrease the orientation of Goss {110} <001> and the secondary recrystallized grains cannot grow sufficiently. In the invention, then, the rate of temperature rise S2 at 600 to 700 ° C is made no more than 0.6 x S1 ° C / s, less than the rate of temperature rise defined by S1.
    [0045] Conversely, when the rate of temperature rise
    Petition 870180068354, of 08/07/2018, p. 18/45
    15/35 at 600 to 700 ° C is less than 30 ° C / s, the <111> recrystallizable orientation subsequent to the Goss {110} <001> orientation increases, and therefore there is a fear of thickening the secondary recrystallized grains . The above is the reason why S2 is made not less than 30 ° C / s, but not more than 0.6 x S1 ° C / s. Preferably, the lower limit of S2 is 50 ° C / s, and the upper limit of this is 0.55 x S1 ° C / s.
    [0046] Thus, the decrease in the rate of temperature rise S2 in the high temperature zone has a beneficial influence not only on the crystal orientation, but also on the coating formation. Because, although the coating formation starts at approximately 600 ° C in the heating process, if rapid heating is conducted in that temperature zone, the remoaming treatment is carried out in a state in which the initial oxidation is absent, so that Violent oxidation occurs during re-soaking and, therefore, subscale silica (S1O2) takes the form of dendrites extended in the form of a rod towards the interior of the steel plate. If the finish annealing is carried out in such a state, S1O2 hardly moves to the surface and free forsterite generates inside the iron matrix, which results in the deterioration of the magnetic properties or coating properties. Thus, the harmful effects above rapid heating can be avoided by decreasing S2.
    [0047] In Patent Documents 1 to 4, a technique is described to improve the conditions of the atmosphere during heating. In these documents, however, the rapid heating is performed in a high temperature zone of 600 to 700 ° C, so that there is a variation in the temperature of the range at the end of the rapid heating and it is difficult to control the shape of the subscale. Therefore, the uniformity of the subscale on a product coil cannot be ensured and it is difficult to obtain a product plate with excellent magnetic properties and coating properties along its length.
    Petition 870180068354, of 08/07/2018, p. 19/45
    16/35 total.
    [0048] In addition, the primary recrystallization annealing can be conducted according to the usual manner and the other conditions in the primary recrystallization annealing after the final cold lamination, such as the recovery temperature, the recovery time, the atmosphere in cleaning, cooling rate and the like are not particularly limited.
    [0049] In general, primary recrystallization annealing is often performed in combination with decarburization annealing. Even in the invention, primary recrystallization annealing combined with decarburization annealing can be conducted, but decarburization annealing can be carried out separately after primary recrystallization annealing.
    [0050] In addition, nitriding is generally performed before or after annealing primary recrystallization or during annealing primary recrystallization to reinforce an inhibitor. Even in the invention, it is possible to apply nitriding.
    Annealing Separator [0051] The steel sheet after primary recrystallization annealing or after decarburization annealing is subjected to the application of an annealing separator and finishing annealing to conduct secondary recrystallization. As the characteristic of the invention, the content of secondary ingredients added to the annealing separator is adjusted to an appropriate range in response to the rate of temperature rise S2, while the secondary ingredient is limited to an element having an ion radius of 0.6 to
    1.3 Â and an attraction force between ion and oxygen of not more than 0.7 Â ' 2 . The elements that satisfy these conditions are Ca, Sr, Li and Na. They can be added alone or in a combination of two or more.
    Petition 870180068354, of 08/07/2018, p. 20/45
    17/35 [0052] The reason why the ionic radius of the added secondary ingredients is limited to the range of 0.6 to 1.3 Â is due to the fact that it is close to an ionic radius of 0.78 Â for the ion MgO magnesium which is a main ingredient of the annealing separator. That is, the coating-forming reaction is a forsterite-forming reaction by moving Mg 2+ or O 2- in the annealing separator through diffusion to react with S1O2 on the steel sheet surface as follows:
    [0053] 2 MgO + S1O2 -> Mg2SiO 4 [0054] When introducing the element having an ionic radius from the above range, the above reaction can be promoted because the Mg 2+ ion is replaced by the above ions during the annealing finish, while the truss defect is introduced in MgO trusses due to truss failure resulting from the difference in ionic radius to easily cause diffusion. When the ionic radius is too large or too small over the above range, the Mg 2+ ion replacement reaction is not caused and therefore the reaction promoting effect cannot be expected.
    [0055] The ionic beam acts towards the MgO side as mentioned above, with the attraction force between the ion and oxygen being a value represented by 2Z / (R, + R o ) 2 when an ionic beam of an atom is Ri and its valence is Z and an ionic ray of the oxygen ion is R o and its valence is 2, which is an indication that shows a degree of action mainly on S1O2 of the subscale with the addition of the secondary ingredient. Concretely, as the value becomes lower, the enrichment of S1O2 in the surface layer is promoted during the annealing finish.
    [0056] That is, S1O2 is considered to move towards the surface layer of the steel plate through the process of dissociation and aggregation such as Ostwald maturation in the formation of the coating. In this case, when an ion having an attractive force between
    Petition 870180068354, of 08/07/2018, p. 21/45
    18/35 the ion and oxygen of not more than 0.7 Â -2 is introduced, the S1O2 bond is cut to easily cause the dissociation process and S1O2 is enriched in the surface layer to improve a chance of contact with MgO and promote the forsterite formation reaction. However, when the force of attraction between the ion and oxygen exceeds 0.7 Â ' 2 , the above effect is not achieved.
    [0057] Also, it is necessary that the content of the ingredient in the annealing separator satisfying the above conditions be controlled for a range satisfying the following equation (1):
    0.01 x S2 - 5.5 <Ln (W) <0.01 x S2 - 4.3 ... (1) [0058] In response to the rate of temperature rise S2 in the high temperature zone of the annealing of primary recrystallization when an amount of addition to MgO is W (mol%).
    [0059] When the rate of temperature rise S2 in the high temperature zone is very high, the resulting dendrite silica (S1O2) subscales deeply below the surface layer of the steel plate, so it is necessary to promote movement of S1O2 to the surface of the steel sheet during annealing finishing, increasing the amount of addition of the secondary ingredient. In contrast, when S2 is very low, dendrite silica does not penetrate deeply, so that S1O2 can move to the surface of the steel plate even if the amount of addition of the secondary ingredient is small. Then, the amount of addition W of the secondary ingredient is required to be adjusted to an appropriate range in response to the rate of temperature rise S2. When W is less than the range of equation (1), the effect of promoting the movement of S1O2 to the surface is not obtained, whereas when it exceeds the range of equation (1), the movement of S1O2 to the surface progresses and the formation of forsterite is deteriorated to cause poor appearance of the coating. Preferably, the limit
    Petition 870180068354, of 08/07/2018, p. 22/45
    The lower 19/35 of Ln (W) is 0.01 x S2 - 5.2 and the upper limit of this is 0.01 x S2-4.5.
    [0060] As the secondary ingredient added to the annealing separator, oxide, borate, conventionally well-known titanium chloride or similar can be added in addition to the elements mentioned above. They have an effect of improving the magnetic properties and an effect of increasing the amount of the coating by additional oxidation, and also these effects are independent of the above secondary ingredient, so that they can be added in a compound form.
    [0061] Furthermore, the annealing separator is preferably applied in an amount of 8 to 14 g / m 2 on both surfaces as a slurry-like coating liquid in order to have a hydrated ignition loss of 0.5 to 3 , 7% by mass, and then dried.
    [0062] In the production method of electric grain-oriented steel sheet according to the invention, the magnetic domain refinement treatment of radiating laser, plasma, electron beams or similar can be performed after finishing annealing and formation of insulation coating. In particular, the means for reinforcing the coating according to the invention can be used effectively in the method of radiating electron beams. That is, the irradiation of electron beams is responsible for easily exfoliating the coating because the electron beams transmit the coating to raise the surface temperature of the steel sheet. On the contrary, according to the invention, the homogeneous and strong coating can be formed promoting the reaction of forsterite formation, and the exfoliation of the coating with the irradiation of electron beams can be suppressed.
    Example 1 [0063] A steel plate containing C: 0.06% by weight, Si: 3.3%
    Petition 870180068354, of 08/07/2018, p. 23/45
    20/35 by mass, Mn: 0.08% by mass, S: 0.023% by mass, sol, Al: 0.03% by mass, N: 0.007% by mass, Cu: 0.2% by mass and Sb : 0.02% by mass is heated to 1,430 ° C and remolted for 30 minutes and then hot rolled to form a hot rolled sheet having a thickness of 2.2 mm, which is subjected to an annealing of 1000 ° C by 1 minute and then cold rolled to form a cold rolled sheet having a thickness of 0.23 mm. Then, the plate is heated by changing a temperature rise range S1 between 500 ° C and 600 ° C and a temperature rise rate S2 between 600 ° C and 700 ° C, respectively, as shown in Table 1 and then subjected to primary recrystallization annealing combined with decarburization annealing at 840 ° C for 2 minutes. Then, an annealing separator slurry composed mainly of MgO and containing 10% by mass of T1O2 and a variable amount of a secondary ingredient (s) having different ionic rays and ion-oxygen attraction forces as shown in Table 1 in the form of an oxide it is applied to the plate in an amount of 12 g / m 2 (by both surfaces) in order to make a loss of ignition hydrated by 3.0% by mass, and then the plate it is dried, wound in a coil, subjected to finishing annealing, followed by the application of a coating liquid of magnesium phosphate-colloidal silica-chromic anhydride-silica powder and then subjected to annealing finishing combined with cooking of the coating liquid and narrowing the shape of the steel sheet at 800 ° C for 30 seconds to obtain a coil of product.
    [0064] From the product coil thus obtained, test specimens are repeatedly collected at a given interval in the longitudinal direction to measure ionic loss along the total length of the coil, from which a ratio of a part having a ionic loss W17 / 50 of no more than 0.80 W / kg over the
    Petition 870180068354, of 08/07/2018, p. 24/45
    21/35 total length of the product reel. Also, the surface of the steel plate is visually inspected during the collection of the test specimen to confirm the presence or absence of coating failure such as color shading, spot-like coating defect or the like, from which a ratio is determined. of non-defective parts having no coating failure along the entire length.
    [0065] The results are also shown in Table 1. As seen from these results, the steel sheets of the Examples of the invention produced under conditions of rate of temperature rise and the addition of the secondary ingredient in the annealing separator adaptable to the invention have good magnetic properties and coating properties because the ratio of W17 / 50 0.80 W / kg is not less than 70% and the ratio of parts having a good coating appearance is not less than 99% over the total length.
    Petition 870180068354, of 08/07/2018, p. 25/45
    22/35
    Comments Comparative Example Comparative Example Comparative Example Comparative Example Comparative Example Comparative Example Comparative Example Comparative Example List of good parts in the product (%) Coating property 66 66 100 100 66 100 100 100 Tonic loss property O O O O O O O O Secondary ingredient (s) in the annealing separator Ln (W) -5.3 -4.8 -4.5 CN 'T -5.3 -4.8 -4.5 CN 'T W content (mol%) 0.005 CO o o o the o 0.015 0.005 CO o o o the o 0.015 Ionoxygen attraction force (Â 2 ) 0.62 0.62 0.62 0.62 0.62 0.62 0.62 0.62 Ionic radius(THE) Element type Here Here Here Here Here Here Here Here Primary recrystallization annealing temperature rise rate S2 / S1 0.25 0.50 0.75 the o 0.19 CO CO o 0.75 the o S2 (° C / s) LOI O | m | 20 m | 30 09 the CO 'tn to O o 20 08 At the. - CN COm CDCO
    Petition 870180068354, of 08/07/2018, p. 26/45
    23/35
    Comments Comparative Example Example ofInvention Example ofInvention Example ofInvention Example ofInvention Comparative Example Comparative Example List of good parts in the product (%) Coating property 100 100 100 100 100 66 86 Ionic loss property 30 70 85 06 75 09 35 Secondary ingredient (s) in the annealing separator Ln (W) -5.3 -4.6 CN 1 -4.0 -3.9 -3.9 W content (mol%) 0.005 o o o 0.015 0.017 0.019 0.020 0.021 Ionoxygen attraction force (Â -2 ) 0.62 0.62 0.62 0.62 0.62 0.62 0.62 Ionic radius(THE) Element type Here Here Here Here Here Here Here Primary recrystallization annealing temperature rise rate S2 / S1 0.20 0.30 the o 0.50 0.60 0.70 the o S2 (° C / s) 20 30 40 50 09 70 100 'tn ω o o 100 At the. CD O - CN COm
    Petition 870180068354, of 08/07/2018, p. 27/45
    24/35
    Comments Comparative Example Example ofInvention Example ofInvention Example ofInvention Example ofInvention Comparative Example Comparative Example List of good parts in the product (%) Coating property 66 100 100 100 100 86 95 Ionic loss property 45 06 100 95 O00 55 50 Secondary ingredient (s) in the annealing separator Ln (W) -5.3 -4.6 CN -3.9 CO1 -3.6 -3.5 W content (mol%) 0.005 o o o 0.015 0.020 0.025 0.028 0.030 Ionoxygen attraction force (Â -2 ) 0.62 0.62 0.62 0.62 0.62 0.62 0.62 Ionic radius(THE) Element type Here Here Here Here Here Here Here Primary recrystallization annealing temperature rise rate S2 / S1 the o 0.15 0.25 0.50 0.60 0.70 the o S2 (° C / s) 20 30 50 100 120 140 200 7n ω o o 200 At the. CD00 CD 20 CN 22
    Petition 870180068354, of 08/07/2018, p. 28/45
    25/35
    Comments Comparative Example Example ofInvention Example ofInvention Example ofInvention Comparative Example Comparative Example List of good parts in the product (%) Coating property 100 100 100 100 95 93 Ionic loss property 40 85 95 100 55 50 Secondary ingredient (s) in the annealing separator Ln (W) -5.3 -4.6 CN -3.0 -2.3 1 W content (mol%) 0.005 o o o 0.015 0.050 the oO 0.250 Ionoxygen attraction force (Â 2 ) 0.62 0.62 0.62 0.62 0.62 0.62 Ionic radius(THE) 1.14 1.14 1.14 1.14 1.14 1.14 Element type Here Here Here Here Here Here Primary recrystallization annealing temperature rise rate S2 / S1 0.05 CO o o 0.13 0.50 0.63 the o S2 (° C / s) 20 30 50 200 250 400 'tn ω o o 400 At the. 23 24 25 26 27 28
    Petition 870180068354, of 08/07/2018, p. 29/45
    26/35
    Comments Example ofInvention Comparative Example Example ofInvention Example ofInvention Comparative Example Comparative Example List of good parts in the product (%) Coating property the o ID the o the o the CO O Ionic loss property m CD the CO the o the CD O00 ID00 Secondary ingredient (s) in the annealing separator Ln (W) CD1 CD1 CD1 CD1 CD1 CD1 W content (mol%) OO o OO o OO o OO o OO o OO o Ionoxygen attraction force (Â 2 ) ID ID o 00 o 00 CO o CO o CO CN o CD Ionic radius(THE) CO the ID 00 00 o CD CN ID CO 00 o Element type ώ cu tn □ cu zc ω Primary recrystallization annealing temperature rise rate S2 / S1 O o the o the o the o O o the o S2 (° C / s) O O O O O O 'ω' ω ω ο O o At the. CD CN the CO CO CN CO COCONUT CO
    Petition 870180068354, of 08/07/2018, p. 30/45
    27/35
    Comments Comparative Example Example ofInvention Example ofInvention Example ofInvention Example ofInvention Comparative Example Comparative Example List of good parts in the product (%) Coating property 100 100 100 100 100 66 95 Ionic loss property 50 75 95 O00 75 65 30 Secondary ingredient (s) in the annealing separator Ln (W) -5.3 -4.6 CN 'T 1 -4.0 -3.9 -3.9 W content (mol%) 0.005 o o o 0.015 0.017 0.019 0.020 0.021 Ionoxygen attraction force (Â 2 ) 1 1 1 1 1 1 1 Ionic radius(THE) 1 1 1 1 1 1 1 Element type Ca + Sr Ca + Sr Ca + Li Ca + Na Ca + Sr Sr + Li Ca + Li Primary recrystallization annealing temperature rise rate S2 / S1 0.20 0.30 o φo 0.50 0.60 0.70 the o S2 (° C / s) 20 30 40 50 09 70 100 Tn ω o o 100 At the. 35 36 37 0000 39 40 5-
    Petition 870180068354, of 08/07/2018, p. 31/45
    28/35
    Comments Comparative Example Example ofInvention Comparative Example List of good parts in the product (%) Coating property 09 100 65 Ionic loss property 09 06 75 Secondary ingredient (s) in the annealing separator Ln (W) -5.8 -4.6W content (mol%) 0.003 o o o 0.025 Ionoxygen attraction force (Â 2 ) 1 1 1 Ionic radius(THE) 1 1 1 Element type Ca + Li Ca + Li Ca + Li Primary recrystallization annealing temperature rise rate S2 / S1 0.30 the o 0.50 S2 (° C / s) 30 40 50 7n ω o o 100 At the. 42 43 44
    Petition 870180068354, of 08/07/2018, p. 32/45
    29/35
    Example 2 [0066] A steel plate having a chemical composition shown in Table 2 is heated to 1,430 ° C and remolted for 30 minutes and hot rolled to form a hot rolled plate having a thickness of 2.2 mm, which is subjected to annealing at 1,000 ° C for 1 minute, cold rolled to a thickness of 1.5 mm, subjected to intermediate annealing at 1,100 ° C for 2 minutes and still cold rolled to form a cold rolled sheet having a thickness end of 0.23 mm. The cold-rolled sheet is subjected to refinement treatment in the magnetic domain for the formation of linear grooves by electrolytic deposition and heated to 700 ° C under the condition that a temperature rise rate S1 between 500 ° C and 600 ° C is 200 ° C / s and a temperature rise range S2 between 600 ° C and 700 ° C is 50 ° C / s, and then subjected to primary recrystallization annealing combined with decarburization annealing at 840 ° C in an atmosphere having PH2O / PH2 0.4 for 2 minutes. Then, an annealing separator slurry composed mainly of MgO and containing 10% by mass of T1O2 and a variable amount of a Li oxide having an ionic radius of 0.88 Å and an ion-oxygen attraction force 0.38 Â ' 2 is applied to the plate in an amount of 12 g / m 2 (for both surfaces) in order to make a loss of ignition hydrated by 3.0% by mass, and then the plate is dried, wound in a coil, subjected to finishing annealing, followed by the application of a coating liquid of magnesium phosphate-colloidal silica-chromic anhydride-silica powder and then subjected to flattening annealing combined with cooking of the coating liquid and narrowing of the shape of the steel plate at 800 ° C for 20 seconds to obtain a coil of product.
    [0067] From the product reel thus obtained, test specimens are repeatedly collected at a given interval in the direction
    Petition 870180068354, of 08/07/2018, p. 33/45
    30/35 longitudinal, which are subjected to stress relief annealing at 800 ° C in a nitrogen atmosphere for 3 hours and then a W17 / 50 magnetic loss is measured by an Epstein test to determine a ratio of a part having a magnetic loss W17 / 50 of no more than 0.80 W / kg over the entire length of the product spool. Also, the surface of the steel plate is visually inspected during the collection of the test specimen to confirm the presence or absence of failure in the coating such as color shading, spot-like coating defect or similar, from which a list of parts non-defective with no coating failure over the entire length.
    [0068] The results are also shown in Table 2. As seen from these results, the steel sheets of the Examples of the invention produced under conditions of rate of temperature rise and addition of the secondary ingredient in the annealing separator adaptable to the invention have good magnetic properties and coating properties because the ratio of W17 / 50 0.80 W / kg is not less than 70% and the ratio of parts having a good coating appearance is not less than 99% over the total length.
    Petition 870180068354, of 08/07/2018, p. 34/45
    31/35
    Comments Example of the Invention Example of the Invention Example of the Invention Example of the Invention Example of the Invention Example of the Invention Example of the Invention Example of the Invention Example of the Invention Example of the Invention Steel sheet properties Good coating ratio (%) CD CD A CD CD A CD CD A CD CD A CD CD A CD CD A CD CD A CD CD A CD CD A CD CD A Good ratio in magnetic loss (%) The CD CO ID CD ID CD ID O O O O O O CD ID CD ID O O Annealing separator Ln(W) CD1 CD1 CD1 CD1 CD1 CD1 CD1 CD1 CD1 CD1 Li content (% in mol) O o O o O o O o O o O o O o O o O o O o Chemical composition of the steel sheet (% by mass) Others 1 1 Cu: 0.2 OThe Li O OOZ Ni: 0.8,Sb: 0.005 O_Q ω Sb: 0.005,Sn: 0.005 Mo: 0.5 Bi: 0.001 z the o the o the o the o O o the o O o the o the o the o Al sol. 0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.03 φ ω+ ω 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 φ ω 0.02 1 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 ω 1 0.02 1 1 1 1 1 1 1 1O O O O O O O O O O ω CO CO CO CO CO C * 3 CO C * 3 CO CO ο O O O O O O O O O O At the. - CN COID CD 1 ^ 00 CD O
    Petition 870180068354, of 08/07/2018, p. 35/45
    32/35
    Comments Example of the Invention Example of the Invention Example of the Invention Example of the Invention Comparative Example Comparative Example Comparative Example Comparative Example Steel sheet properties Good coating ratio (%) CD CD A CD CD A CD CD A CD CD A CN CD 00 CD 00 ID CD Good ratio in magnetic loss (%) O O O O CD ID CD ID O ID O00 O00 Annealing separator Ln(W) CD1 CD1 CD1 CD1 3 3 Li content (% in mol) O o O o O o O o 0.005 0.0050.03 0.03 Chemical composition of the steel sheet (% by mass) Others O O o ώ P: 0.06 O o_Q Z V: 0.02 1 Sb: 0.005,Sn: 0.005 1 Sb: 0.005,Sn: 0.005 z the o the o O o the o the o the o the o the o Al sol. 0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.03 φ ω+ ω 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 φ ω 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 ω 1 1 1 1 1 1 1 1O O O O O O O O ω CO CO CO CO C * 3 CO CO CO ο O O O O O O O O At the. - CN COID CD00
    Petition 870180068354, of 08/07/2018, p. 36/45
    33/35
    Example 3 [0069] A steel plate containing C: 0.06 mass%, Si: 3.3 mass%, Mn: 0.08 mass%, S: 0.023 mass%, sol, Al: 0, 03% by mass, N: 0.007% by mass, Cu: 0.2% by mass and Sb: 0.02% by mass is heated to 1,430 ° C and remolted for 30 minutes and hot rolled to form a laminated plate. hot having a thickness of 2.2 mm, which is subjected to annealing at 1000 ° C for 1 minute and cold rolled to form a cold rolled sheet having a thickness of 0.23 mm. The sheet is then subjected to primary recrystallization annealing by heating to 700 ° C under such a condition that a rate of temperature rise S1 between 500 ° C and 600 ° C is 200 ° C / s and a rate of temperature rise S2 between 600 ° C and 700 ° C it is 50 ° C / s and then cooling as primary recrystallization annealing and decarburization annealing at 840 ° C in an atmosphere of PH2O / PH2 = 0.4 for 2 minutes. Then, an annealing separator slurry composed mainly of MgO and containing 10% by mass of T1O2, 5% by mass of magnesium sulphate and a variable amount of a Sr oxide having an ionic radius of 1.3 Â and an ionoxygen attraction force of 0.55 Â ' 2 is applied to the plate in an amount of 12 g / m 2 (across both surfaces) in order to make hydration loss of ignition by 3.0% by mass, and then the sheet is dried, wound in a coil, subjected to annealing, followed by the application of a chromium magnesium phosphate-silica-colloidal anhydride-silica powder coating liquid and then subjected to flattening annealing combined with cooking of the coating liquid and narrowing of the shape of the steel plate at 800 ° C for 20 seconds and further refinement treatment in the magnetic domain to obtain a product coil.
    [0070] From the product reel thus obtained, a sample is collected
    Petition 870180068354, of 08/07/2018, p. 37/45
    34/35 test piece of cut sheet along the length to measure the loss of W17 / 50 ions by the SST (Single Sheet Tester) testing machine, while a 1000 kVA oil-filled transformer is manufactured from the coil of remaining product to measure ionic loss in the actual transformer. Also, the surface of the steel sheet is visually inspected along the entire length of the coil during the collection of the cut sheet test piece along the length to confirm the presence or absence of failure in the coating such as color shading, point-like or similar coating, from which a ratio of non-defective parts is determined, with no coating failure along the entire length.
    [0071] The results are also shown in Table 3. As seen from these results, the steel sheets of the Examples of the invention produced under conditions of rate of temperature rise and the secondary ingredient in the annealing separator adaptable to the invention are not only excellent in terms of magnetic loss properties and coating properties of the product coil, but also have a low construction factor (BF: transformer magnetic loss ratio for steel plate magnetic loss) and have good magnetic loss properties after the transformer assembly.
    Petition 870180068354, of 08/07/2018, p. 38/45
    35/35
    Comments Comparative Example Example of the Invention Comparative Example Transformer properties BF 1.23 1.09 1.21 Magnetic loss W17 / 50 (W / kg) 0.97 CO o 0.94 Steel sheet properties Good coating ratio (%) 100 100 100 Average magnetic loss of test piece cut along lengthW17 / 50 (W / kg) 0.79 0.74 00 o Annealing separator Ln (W) -5.3 -4.1Sr contentW (mol%) 0.005 0.017 0.025 At the. - CN CO
    Petition 870180068354, of 08/07/2018, p. 39/45
    1/2
    权利要求:
    Claims (5)
    [1]
    1. Method for producing an electric grain steel sheet oriented by hot rolling a steel sheet of a chemical composition comprising C: 0.001 to 0.10% by weight, Si: 1.0 to 5.0% by weight , Mn: 0.01 to 1.0% by weight, at least one of S and Se: 0.01 to 0.05% by weight in total, Al sol .: 0.003 to 0.050% by weight, N: 0.001 to 0.020% by mass and the balance being Fe and unavoidable impurities, undergoing a single cold rolling or two or more cold rolling including an intermediate annealing between them to a final thickness and also a primary recrystallization annealing, application of an annealing separator composed mainly of MgO and a finishing annealing, characterized by the fact that in the primary recrystallization annealing, a temperature rise rate S1 between 500 and 600 ° C is made not less than 100 ° C / s , and a rate of temperature rise S2 between 600 and 700 ° C is made 30 ° C / s to 0.6 x S1 ° C / s, while the total content W (% in mol) of an element having an ionic radius of 0.6 to 1.3 A and an attraction force between ion and oxygen of not more than 0.7 A -2 included in the MgO annealing separator is adjusted to satisfy the following equation (1 ) in relation to S2:
    0.01 S2 - 5.5 <Ln (W) <0.01 S2 - 4.3 (1)
    [2]
    2. Method for producing a grain-oriented electric steel sheet according to claim 1, characterized by the fact that decarburization annealing is performed after primary recrystallization annealing.
    [3]
    3. Method for producing a grain-oriented electric steel plate, according to claim 1 or 2, characterized by the fact that the element having an ionic radius of 0.6 to 1.3 A and an attraction force between the ion and oxygen of not more than 0.7 A -2 is at least one among Ca, Sr, Li and Na.
    Petition 870180068354, of 08/07/2018, p. 40/45
    2/2
    [4]
    4. Method for producing a grain-oriented electric steel plate according to any one of claims 1 to 3, characterized by the fact that, in addition to the chemical composition above, the steel plate contains at least one selected from Cu: 0.01 to 0.2 wt%, Ni: 0.01 to 0.5 wt%, Cr: 0.01 to 0.5 wt%, Sb: 0.01 to 0.1 wt%, Sn: 0.01 to 0.5% by mass, Mo: 0.01 to 0.5% by mass and Bi: 0.001 to 0.1% by mass.
    [5]
    5. Method for producing a grain-oriented electric steel sheet according to any one of claims 1 to 4, characterized by the fact that, in addition to the above chemical composition, the steel sheet contains at least one selected from B: 0.001 to 0.01% by mass, Ge: 0.001 to 0.1% by mass, As: 0.005 to 0.1% by mass, P: 0.005 to 0.1% by mass, Te: 0.005 to 0, 1% by mass, Nb: 0.005 to 0.1% by mass, Ti: 0.005 to 0.1% by mass, and V: 0.005 to 0.1% by mass.
    Petition 870180068354, of 08/07/2018, p. 41/45
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    KR101499404B1|2015-03-05|
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    JP5360272B2|2013-12-04|
    US20150007908A1|2015-01-08|
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    法律状态:
    2018-05-15| B06A| Notification to applicant to reply to the report for non-patentability or inadequacy of the application according art. 36 industrial patent law|
    2018-09-18| B09A| Decision: intention to grant|
    2018-11-06| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 15/08/2012, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    JP2011178841|2011-08-18|
    JP2011-178841|2011-08-18|
    JP2012161139A|JP5360272B2|2011-08-18|2012-07-20|Method for producing grain-oriented electrical steel sheet|
    JP2012-161139|2012-07-20|
    PCT/JP2012/070758|WO2013024874A1|2011-08-18|2012-08-15|Method for producing oriented electromagnetic steel sheet|
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