Title of invention: Directional electromagnetic steel sheet and its manufacturing method
Technical field
[0001]
　The present invention relates to a grain-oriented electrical steel sheet used as an iron core material of a transformer and a method for manufacturing the same, and in particular, a grain-oriented electrical steel sheet having excellent adhesion of a tension insulating film and a method for manufacturing the same.
Background technology
[0002]
　The grain-oriented electrical steel sheet is a silicon steel sheet containing 7% by mass or less of Si, which is composed of crystal grains highly oriented and accumulated in the {110} <001> direction (hereinafter, Goss direction), and is mainly iron of a transformer. Used as a core material. Highly oriented accumulation of Goss orientation in grain-oriented electrical steel sheets is realized by utilizing a grain growth phenomenon called secondary recrystallization.
[0003]
　Electrical steel sheets are required to have high magnetic flux density (represented by B8 value) and low iron loss (represented by W17 / 50 value) as magnetic characteristics, but recently, from the viewpoint of energy saving. Therefore, there is an increasing demand for reduction of power loss, that is, reduction of iron loss.
[0004]
　In grain-oriented electrical steel sheets, the magnetic domain changes with the movement of the domain wall under an alternating magnetic field. Smooth movement of the domain wall is effective in reducing iron loss, but when observing the movement of the magnetic domain, there are some magnetic domains that do not move.
[0005]
　In order to further reduce the iron loss of the grain-oriented electrical steel sheet, the unevenness of the interface of the forsterite (Mg 2 SiO 4 ) -based film (hereinafter sometimes referred to as “glass film”) on the surface of the steel sheet that hinders the movement of magnetic domains . It is important to eliminate the pinning effect caused by. In order to eliminate this pinning effect, it is an effective means not to form a glass film on the surface of the steel sheet that hinders the movement of magnetic domains.
[0006]
　As a means for eliminating the pinning effect, for example, Patent Documents 1 to 21 describe Fe-based oxides (Fe 2 SiO 4 , FeO, etc. ) in the oxide layer formed during decarburization annealing by controlling the dew point of decarburization annealing. ) Is not formed, and a substance such as alumina that does not react with silica is used as the annealing separator to achieve surface smoothing after finish annealing.
[0007]
　Further, when a grain-oriented electrical steel sheet is used as an iron core material for a transformer, it is essential to ensure the insulating property of the steel sheet, so an insulating film having tension is formed on the surface of the steel sheet. For example, the method disclosed in Patent Document 6 in which a coating liquid mainly composed of colloidal silica and phosphate is applied to the surface of a steel sheet and baked to form an insulating film has a large effect of applying tension to the steel sheet. Therefore, it is effective in reducing iron loss in addition to ensuring insulation.
[0008]
　As described above, forming an insulating film mainly composed of phosphate on the glass film formed in the finish annealing step is a general method for producing a unidirectional silicon steel sheet.
[0009]
　When the above insulating film is formed on the glass film, considerable film adhesion can be obtained, but when the glass film is removed or when the glass film is not intentionally formed in the finish annealing step. The film adhesion is not sufficient.
[0010]
　When the glass film is removed, it is necessary to secure the required film tension only by the tension insulating film formed by applying the coating liquid. Therefore, inevitably, the film must be thickened, and even more. Film adhesion is required.
[0011]
　Therefore, with the conventional film forming method, it is difficult to achieve the film tension sufficient to bring out the effect of mirroring and to secure the film adhesion, and it is possible to sufficiently reduce the iron loss. It wasn't done. Therefore, as a technique for ensuring the film adhesion of the tension insulating film, for example, a method of forming an oxide film on the surface of a finish-annealed unidirectional silicon steel sheet prior to forming the tension insulating film is patented. It was proposed in Documents 22-25.
[0012]
　For example, in the technique disclosed in Patent Document 23, a finish-annealed unidirectional silicon steel sheet prepared to be mirror-finished or close to a mirror surface is annealed at a specific atmosphere at each temperature, and the surface of the steel sheet is surfaced. This is a method in which an external oxide type oxide film is formed on the steel sheet, and the adhesiveness between the tension insulating film and the steel sheet is ensured by this oxide film.
[0013]
　The technique disclosed in Patent Document 24 forms an amorphous oxide base film on the surface of a finish-annealed unidirectional silicon steel sheet without an inorganic mineral film when the tension insulating film is crystalline. This is a technique for preventing the oxidation of the steel sheet, that is, the decrease in the mirror surface, which occurs when the crystalline tension insulating film is formed.
[0014]
　The technique disclosed in Patent Document 25 further develops the technique disclosed in Patent Document 8 to control the film structure of a metal oxide film containing Al, Mn, Ti, Cr, and Si at the interface between the tension insulating film and the steel sheet. This is a method for improving the adhesion of the insulating film. However, the adhesion between the metal oxide layer and the steel sheet, where stress sensitivity is the most problematic, is not controlled, and the technique disclosed in Patent Document 25 is insufficient as a technique for improving film adhesion. is there.
Prior art literature
Patent documents
[0015]
Patent Document 1: Japanese Patent Application
Laid-Open No. 64-062417 Patent Document 2: Japanese Patent Application Laid-Open No. 07-118750
Patent Document 3: Japanese Patent Application Laid-Open No. 07-278668
Patent Document 4: Japanese Patent Application Laid-Open No. 07-278 278669 JP
Patent Document 5: Japanese Unexamined Japanese Patent Application Laid-Open No. 07-278670
Patent Document 6: Japanese Patent Laid-Open 10-046252 discloses
Patent Document 7: Japanese Patent Laid-Open 11-106827 discloses
Patent Document 8: Japanese Patent 11-152517
Patent Document 9: Japanese Patent Application Laid-Open No. 2002-060843
Patent Document 10: Japanese Patent Application Laid-Open No. 2002-173715
Patent Document 11: Japanese Patent Application Laid-Open No. 2002-348613
Patent Document 12: Japan Japanese Patent Application Laid-Open No. 2002-363646
Patent Document 13: Japanese Patent Application Laid-Open No. 2003-055717
Patent Document 14: Japanese Patent Application Laid-Open No. 2003-268541
Patent Document 15: Japanese Patent Application Laid-Open No. 2003-003213
Patent Document 16: Japanese Patent Application Laid-Open No. 2003-041320
Patent Document 17: Japanese Patent Application Laid-Open No. 2003-247021
Patent Document 18: Japanese Patent 2003-247024 JP
Patent Document 19: Japanese Patent 2008-001980 JP
Patent Document 20: Japanese Kohyo 2011-518253 JP
Patent Document 21: Japanese Sho 48- 039338
Patent Document 22: Japanese Patent Application
Laid-Open No. 60-131976 Patent Document 23: Japanese Patent Application Laid-Open No. 06-184762
Patent Document 24: Japanese Patent Application Laid-Open No. 07-278833
Patent Document 25: Japanese Patent Application Laid-Open No. 069338 Kai 2002-348643
Non-patent literature
[0016]
Non-Patent Document 1: Iron and Steel, vol99 (2013) 40.
Outline of the invention
Problems to be solved by the invention
[0017]
　In a grain-oriented electrical steel sheet in which a tension insulating film is formed on the surface of a steel sheet, when the insulating film is formed on a glass film (forsterite-based film), the film adhesion of the insulating film is good, but the glass film has good adhesion. When the formation is intentionally suppressed, the glass film is removed by means such as search or pickling, or the surface of the steel sheet is flattened until it has a mirror gloss to form a tension insulating film, the insulating film is formed. The film adhesion is not sufficient, and it is difficult to achieve both film adhesion and magnetic stability.
[0018]
　Therefore, in the present invention, the formation of a glass film is intentionally suppressed, the glass film is removed by means such as grinding or pickling, and the surface of the steel sheet is flattened until it has a mirror gloss. The object is to form a tension insulating film with excellent film adhesion on the surface of the grain-oriented electrical steel sheet without impairing its magnetic properties and its stability. The purpose is to provide a method.
Means to solve problems
[0019]
　In order to solve the above problems, the present inventors have diligently studied a method for improving the film adhesion of the tension insulating film, focusing on the influence of additive elements. As a result, prior to the formation of the tension insulating film, an oxide film (hereinafter, may be referred to as "intermediate oxide film layer" or "SiO 2 intermediate oxide film layer") is formed on the surface of the finish-annealed directional electromagnetic steel plate . It was found that controlling the thermal history and oxygen partial pressure in the forming process dramatically improves the film adhesion of the tension insulating film.
[0020]
　Furthermore, the present inventors have diligently investigated the composition of the intermediate oxide film layer, which is considered to have the greatest effect on the film adhesion. As a result, the oxide of the intermediate oxide film layer is Si oxide (SiO 2 ), and when an element such as Mn is solid-dissolved in the SiO 2 intermediate oxide film layer, the film adhesion is improved. I found it.
[0021]
　SiO 2 atoms in solid solution in the intermediate oxide layer is, SiO 2 improve lattice matching with the intermediate oxide layer and the steel plate, as a result, SiO 2 considered adhesion of the intermediate oxide layer is improved Be done.
[0022]
　The present invention has been made based on the above findings, and the gist thereof is as follows.
[0023]
　[1] The grain-oriented electrical steel sheet according to one aspect of the present invention is an intermediate steel sheet formed on a base steel sheet and the base steel sheet , containing SiO 2 and having an average film thickness of 1.0 nm to 1.0 μm. It includes an oxide film layer and a tension insulating film formed on the intermediate oxide film layer.
　The base steel sheet has C: 0.010% or less, Si: 2.50 to 4.00%, acid-soluble Al: 0.010% or less, N: 0.012% or less in mass% as chemical components. , Mn: 1.00% or less, S: 0.020% or less, and the balance is composed of Fe and impurities.
　SiO 2 by the reflection type infrared spectroscopic analysis of the surface of the intermediate oxide layer, 1250 cm -1 peak intensity I A and, 1200 cm -1 peak intensity I B satisfies the following equation (1).
　I B / I A ≧ 0.010 · · · (1)
[0024]
　[2] The grain-oriented electrical steel sheet according to the above [1] may further contain B: 0.001 to 0.010% in mass%.
[0025]
　[3] The grain-oriented electrical steel sheet according to the above [1] or [2] further has Sn: 0.01 to 0.20%, Cr: 0.01 to 0.50%, Cu: in mass%. It may contain 0.01 to 0.50% of one kind or two or more kinds.
[0026]
　[4] The directional electromagnetic steel plate according to any one of the above [1] to [3] has glow discharge emission of the element M (M: Mn, Al, B) on the surface of the SiO 2 intermediate oxide film layer. The time derivative curve f M (t) of the analysis spectrum may satisfy the following equation (2).
[0027]
[Number 1]

[0028]
　　Tp: Time t (seconds) corresponding to the minimum value of the second-order time derivative curve of the glow discharge emission analysis spectrum of
　　Si Ts: Time t (seconds) corresponding to the start point of the glow discharge emission analysis of Si
[0029]
　[5] The method for producing a grain-oriented electrical steel sheet according to another aspect of the present invention is the method for producing a grain-oriented electrical steel sheet according to any one of the above [1] to [4]. It has an oxide film forming step of forming an intermediate oxide film layer on the surface of a steel sheet.
　In the oxide film forming step, the annealing temperature T1: 600 to 1200 ° C., the annealing time: 5 to 200 seconds, the oxygen partial pressure PH2O / PH2 : 0.15 or less, and the average heating rate in the temperature range of 100 ° C. to 600 ° C. Annealing is performed under the condition of HR 1:10 to 200 ° C., and after the annealing, the average cooling rate CR1 in the temperature range of T2 ° C to T1 ° C is set to 50 ° C. The speed CR2 is set to less than CR1. Here, T2 ° C represents the temperature represented by T1 ° C-100.
Effect of the invention
[0030]
　According to the present invention, the formation of a glass film is intentionally suppressed, the glass film is removed by means such as grinding or pickling, and the surface of the steel sheet is flattened until it has a mirror gloss. A tension-applying insulating film having excellent film adhesion can be formed on the surface of the unidirectional silicon steel sheet without impairing the magnetic properties and its stability.
A brief description of the drawing
[0031]
FIG. 1 is a diagram showing an example of a reflective infrared spectroscopic analysis spectrum on the surface of a SiO 2 intermediate oxide film layer.
Mode for carrying out the invention
[0032]
　The grain-oriented electrical steel sheet of the present invention (hereinafter sometimes referred to as “the electrical steel sheet of the present invention”) is formed on a base steel sheet and the base steel sheet , contains SiO 2 , and has an average film thickness of 1.0 nm. It includes an intermediate oxide film layer having a thickness of about 1.0 μm and a tension insulating film formed on the intermediate oxide film layer.
　The base steel sheet has C: 0.010% or less, Si: 2.50 to 4.00%, acid-soluble Al: 0.01% or less, N: 0.012% or less in mass% as chemical components. , Mn: 1.00% or less, S: 0.02% or less, and the balance is composed of Fe and impurities.
　SiO 2 by the reflection type infrared spectroscopic analysis of the surface of the intermediate oxide layer, 1250 cm -1 peak intensity I A and, 1200 cm -1 peak intensity I B is characterized by satisfying the following formula (1).
　I B / I A ≧ 0.010 · · · (1)
[0033]
　The base steel sheet further contains (a) B: 0.001 to 0.010% and / or (b) Sn: 0.01 to 0.20% and Cr: 0.01 to 0 in mass%. It may contain one or more of .50% and Cu: 0.01 to 0.50%.
[0034]
　In the electromagnetic steel plate of the present invention, the time derivative curve f M (t) of the glow discharge emission analysis spectrum of the element M (M: Mn, Al, B) on the surface of the SiO 2 intermediate oxide film layer satisfies the following formula (2). You may.
[0035]
[Number 2]

[0036]
　　Tp: Time t (seconds) corresponding to the minimum value of the second-order time derivative curve of the glow discharge emission analysis spectrum of
　　Si Ts: Time t (seconds) corresponding to the start point of the glow discharge emission analysis of Si
[0037]
　The method for producing a grain-oriented electrical steel sheet of the present invention (hereinafter, may be referred to as “the manufacturing method of the present invention”) includes an oxide film forming step of forming an intermediate oxide film layer on the surface of the steel sheet, and the oxide film forming step includes an oxide film forming step. Annealing temperature T1: 600-1200 ° C. Annealing time: 5-200 seconds, oxygen partial pressure PH2O / PH2 : 0.15 or less, average heating rate in the temperature range of 100 ° C. to 600 ° C. HR 1:10-200 ° C. After annealing, the average cooling rate CR1 in the temperature range of T2 ° C. to T1 ° C. is set to 50 ° C./sec or less, and the average cooling rate CR2 in the temperature range of 100 ° C. or higher and lower than T2 ° C. is set to less than CR1. To do. Here, T2 ° C represents the temperature represented by T1 ° C-100.
[0038]
　Hereinafter, the electromagnetic steel sheet of the present invention and the manufacturing method of the present invention will be described.
[0039]
　[Base Steel Sheet]
　
　First, the reasons for limiting the component composition of the base material steel sheet will be described. Hereinafter,% related to the component composition means mass%.
[0040]
　C: 0.010% or less When
　C exceeds 0.010%, C suppresses the formation of a concentrated layer of Al and other elements at the interface between the SiO 2 intermediate oxide film layer and the steel sheet. Therefore,
C is set to 0.010% or less. From the viewpoint of improving iron loss characteristics, 0.008% or less is preferable.
Although the lower limit includes 0%, since the detection limit of C is about 0.0001%, 0.0001% is a practical lower limit on a practical steel sheet.
[0041]
　Si: 2.50 to 4.00% If
　Si is less than 2.50%, secondary recrystallization does not proceed sufficiently and good magnetic flux density and iron loss characteristics cannot be obtained. Therefore, Si is 2. 50% or more. It is preferably 2.75% or more, more preferably 3.00% or more.
[0042]
　On the other hand, if Si exceeds 4.00%, the steel sheet becomes brittle and the plate-passability in the manufacturing process is significantly deteriorated. Therefore, Si is set to 4.00% or less. It is preferably 3.75% or less, more preferably 3.50% or less.
[0043]
　Acid-soluble Al: 0.010% or less In the
　slab composition, acid-soluble Al is contained up to 0.07% from the viewpoint of plate-passability in cold rolling. In this sense, the upper limit of acid-soluble Al is 0.07%, but in reality, Al is discharged to the outside of the steel sheet through secondary recrystallization annealing. As a result, the acid-soluble Al contained in the base steel sheet will be 0.010% or less. If it is 0.07% or less, there is no problem in the plate-passability, but the smaller the acid-soluble Al contained in the base steel sheet, the better the iron loss property, preferably 0.006% or less.
Although the lower limit includes 0%, since the detection limit is about 0.0001% as in C, 0.0001% is a substantial lower limit on the practical steel sheet.
[0044]
　N: 0.012% or less If
　N exceeds 0.012%, blister (vacancy) will occur in the steel sheet during cold spreading, and the strength of the steel sheet will increase, resulting in deterioration of sheet permeability during manufacturing. , N is 0.012% or less. It is preferably 0.010% or less, more preferably 0.009% or less.
[0045]
Although the lower limit includes 0%, since the detection limit of N is about 0.0001%, 0.0001% is a substantial lower limit on a practical steel sheet.
[0046]
　Mn: 1.00% or less When
　Mn exceeds 1.00%, the steel undergoes phase transformation during secondary recrystallization annealing, secondary recrystallization does not proceed sufficiently, and good magnetic flux density and iron loss characteristics are obtained. Therefore, Mn is set to 1.00% or less. It is preferably 0.50% or less, more preferably 0.20% or less.
[0047]
　MnS can be utilized as an inhibitor during secondary recrystallization, but when AlN is utilized as an inhibitor, MnS is not essential, so the lower limit of Mn includes 0%. When MnS is used as an inhibitor, Mn is 0.02% or more. It is preferably 0.05% or more, more preferably 0.07% or more.
[0048]
　S: 0.020% or less When
　S exceeds 0.020%, the formation of a concentrated layer of Al and other elements at the interface between the SiO 2 intermediate oxide film layer and the steel sheet is suppressed , as in C. Therefore, S is set to 0.020% or less. It is preferably 0.010% or less.
Although the lower limit includes 0%, since the detection limit of S is about 0.0001%, 0.0001% is a substantial lower limit on a practical steel sheet.
[0049]
　Further, part of the S, may be replaced by Se or Sb, case, S eq = S + 0.406Se, or, S eq using a value obtained by converting at = S + 0.406Sb.
[0050]
　In addition to the above-mentioned elements, the electromagnetic steel sheet of the present invention has (a) B: 0.001 to 0.010% and / or (b) Sn: 0.01 to 0 in order to improve the characteristics of the electrical steel sheet of the present invention. .20%, Cr: 0.01 to 0.50%, Cu: 0.01 to 0.50% may be contained in one or more.
[0051]
　B: 0.001 to 0.010%
　B is concentrated at the interface between the SiO 2 intermediate oxide film layer and the steel sheet (confirmed by the present inventors by GDS), and the film adhesion is achieved. It is an element that contributes to the improvement of. If it is less than 0.001%, the effect of improving the film adhesion cannot be sufficiently obtained, so B is set to 0.001% or more. It is preferably 0.002% or more, more preferably 0.003% or more.
[0052]
　On the other hand, if it exceeds 0.010%, the strength of the steel sheet increases and the passability during cold spreading deteriorates, so B is set to 0.010% or less. It is preferably 0.008% or less, more preferably 0.006% or less.
[0053]
　Sn: 0.01 to 0.20%
　Sn is an element that does not concentrate at the interface between the SiO 2 intermediate oxide film layer and the steel sheet, but contributes to the improvement of film adhesion. The mechanism for improving the film adhesion of Sn is not clear, but as a result of investigating the smoothness of the steel sheet surface after secondary recrystallization, improvement of smoothness was observed. Therefore, Sn reduced the unevenness of the steel sheet surface. It is considered that it contributes to the formation of the interface between the SiO 2 intermediate oxide film layer and the steel sheet , which is smooth and has few unevenness defects .
[0054]
　If it is less than 0.01%, the effect of smoothing the surface of the steel sheet cannot be sufficiently obtained, so Sn is set to 0.01% or more. It is preferably 0.02% or more, more preferably 0.03% or more.
[0055]
　On the other hand, if it exceeds 0.20%, the secondary recrystallization becomes unstable and the magnetic characteristics deteriorate, so Sn is set to 0.20% or less. It is preferably 0.15% or less, more preferably 0.10% or less.
[0056]
　Cr: 0.01 to 0.50%
　Cr is an element that, like B and Cu, is concentrated at the interface between the SiO 2 intermediate oxide film layer and the steel sheet and contributes to the improvement of film adhesion. If it is less than 0.01%, the effect of improving film adhesion cannot be sufficiently obtained, so Cr is set to 0.01% or more. It is preferably 0.03% or more, more preferably 0.05% or more.
[0057]
　On the other hand, if it exceeds 0.50%, Cr may compete for Si and O and inhibit the formation of the SiO 2 intermediate oxide film layer, so Cr is set to 0.50% or less. It is preferably 0.30% or less, more preferably 0.20% or less.
[0058]
　Cu: 0.01 to 0.50%
　Cu is an element that, like B and Cr, is concentrated at the interface between the SiO 2 intermediate oxide film layer and the steel sheet and contributes to the improvement of film adhesion. If it is less than 0.01%, the effect of improving the film adhesion cannot be sufficiently obtained, so the Cu content is set to 0.01% or more. It is preferably 0.03% or more, more preferably 0.05% or more.
[0059]
　On the other hand, if it exceeds 0.50%, the steel sheet becomes brittle during hot rolling, so the Cu content is set to 0.50% or less. It is preferably 0.20% or less, more preferably 0.10% or less.
[0060]
　The rest of the component composition of the base steel sheet is Fe and impurities (unavoidable impurities), but the improvement of magnetic properties, the improvement of properties required for structural members such as strength, corrosion resistance, and fatigue properties, castability and plate-passability Mo, W, In, Bi, Sb, Ag, Te, Ce, V, Co, Ni, Se, Ca, Re, Os, Nb, Zr, Hf for the purpose of improving productivity by using scraps, etc. , Ta, Y, La and the like may be contained in a total amount of 5.00% or less, preferably 3.00% or less, and more preferably 1.00% or less.
[0061]
　[Intermediate oxide film layer]
　Next, an intermediate oxide film layer (hereinafter, may be referred to as a SiO 2 intermediate oxide film layer) that plays an important role in improving film adhesion will be described. The electromagnetic steel sheet of the present invention is manufactured by removing the glass film by means such as grinding or pickling, or intentionally preventing the formation of the glass film. In order to sufficiently secure the film adhesion of the tension insulating film, a SiO 2 intermediate oxide film layer having a required thickness is provided at the interface between the tension insulating film and the steel sheet .
[0062]
Average film thickness of the 　SiO 2 intermediate oxide film layer: 1.0 nm or more and 1.0 μm or less When the average film thickness of the
　SiO 2 intermediate oxide film layer is less than 1.0 nm, sufficient film adhesion of the tension insulating film is ensured. Therefore, the average thickness of the SiO 2 intermediate oxide film layer is set to 1.0 nm or more. It is preferably 5.0 nm or more, more preferably 9.0 nm or more.
[0063]
　On the other hand, if it exceeds 1.0 μm, cracks that are the starting points of fracture occur inside the SiO 2 intermediate oxide film layer, and the film adhesion deteriorates. Therefore, the average film thickness of the SiO 2 intermediate oxide film layer is 1. It shall be 0 μm or less. It is preferably 0.7 μm (= 700 nm) or less, more preferably 0.4 μm (= 400 nm) or less.
[0064]
The thickness of the 　SiO 2 intermediate oxide film layer is measured by observing the sample cross section with a transmission electron microscope (TEM) or a scanning electron microscope (SEM).
[0065]
　The fact that the oxide constituting the SiO 2 intermediate oxide film layer is "SiO 2 " can be confirmed by elemental analysis by TEM or energy dispersive spectroscopy (EDS) associated with SEM.
[0066]
　Specifically, in the EDS spectrum of the SiO 2 intermediate oxide film layer, Si—Kα rays are detected at the position of energy 1.8 ± 0.3 kev on the horizontal axis, and at the same time, the position of 0.5 ± 0.3 kev. The presence of "SiO 2 " can be confirmed by detecting OKα rays . The element can be identified by using Lα ray or Kγ ray in addition to Kα ray.
[0067]
　However, since the EDS spectrum of Si may include a spectrum derived from Si in the steel sheet, to be precise, the surface of the steel sheet is analyzed with an electron microanalyzer (EPMA) to determine whether Si is derived from the steel sheet. It is determined whether it is derived from the SiO 2 intermediate oxide film layer.
[0068]
　Further, SiO 2 surfaces of the intermediate oxide layer was analyzed by reflection infrared spectroscopy, wavenumber 1250 cm -1 ± 20 cm -1 SiO at 2 that peaks derived from the presence, SiO 2 constituting the intermediate oxide layer It can be confirmed that the compound to be used is “SiO 2 ”.
[0069]
　However, since reflective infrared spectroscopic analysis is a method for selectively detecting the compound on the outermost surface of the sample, the analysis is performed on the sample in the absence of the tension insulating film, and (b) the steel plate. For materials having a tension insulating film on the surface, perform this after completely removing the tension insulating film by alkaline cleaning or the like.
[0070]
　Infrared spectroscopy (IR) includes a reflection method and an absorption method. Since the absorption method superimposes the information on the outermost surface of the sample and the information on the inside of the steel sheet , the reflection method is preferable for identifying the compound constituting the SiO 2 intermediate oxide film layer. Further, in the absorption method, the wave number derived from the SiO 2 intermediate oxide film layer does not become 1250 (cm -1 ), and the peak shifts depending on the formation state of SiO 2 .
[0071]
　I B / I A : 0.010 or
　1250 cm -1 peak intensity I of A 1200 cm against -1 peak intensity I B ratio: I B / I A of 0.010 or more.
[0072]
　By controlling the SiO 2 intermediate oxide film layer to 1.0 nm or more and 1.0 μm or less, the film adhesion of the tension insulating film can be ensured, but if there is a lattice defect at the interface between the SiO 2 intermediate oxide film layer and the steel sheet, , The film adhesion may decrease.
[0073]
　Lattice defects at the interface are caused by the difference between the lattice constant of the SiO 2 intermediate oxide film layer and the lattice constant of the steel plate. However, by dissolving Mn in the SiO 2 intermediate oxide film layer, the tension is increased. It is possible to further improve the film adhesion of the insulating film. The mechanism for improving the film adhesion is considered as follows.
[0074]
　SiO 2 on the surface of the intermediate oxide layer, because the dangling bonds (wave function) overhangs derived from Si, SiO 2 surfaces of the intermediate oxide layer, electrical attraction, i.e., will have a suction force .. Thus, SiO 2 is adhered to the intermediate oxide layer and the steel plate, on the one hand, SiO 2 in the interface with the intermediate oxide layer and the steel plate, lattice matching is poor, SiO 2 interface with the intermediate oxide layer and the steel sheet Inevitably, lattice defects are introduced.
[0075]
　However, Mn is, SiO 2 when in solid solution in the intermediate oxide layer, SiO 2 SiO at the interface between the intermediate oxide layer and the steel plate 2 of the grating periodicity is changed, SiO 2 and an intermediate oxide layer and the steel sheet The lattice consistency of the interface is improved. As a result, lattice defects due to lattice mismatch are reduced, and finally, the film adhesion of the tension insulating film is improved.
[0076]
　With the above mechanism , the solid solution state or the concentrated state of Mn in the SiO 2 intermediate oxide film layer, which contributes to the improvement of the film adhesion of the tension insulating film, can be analyzed by the reflective infrared spectroscopic analysis.
[0077]
　In the present invention electrical steel sheet, the wave number 1250 cm -1 , the normal SiO 2 peak is present from further, 1200 cm -1 and 1150 cm -1 , the SiO lattice constant is changed 2 (hereinafter "Si (Mn) O x there.) peak derived from there that ". Then, the lattice constant is changed Si (Mn) O x abundance of wave number 1200 cm -1 or 1150 cm -1 is reflected in the peak intensity of. The wave number, which is the horizontal axis of the reflective infrared spectroscopic analysis, may fluctuate within the range of ± 20 cm -1 depending on the measurement conditions and the fitting method .
[0078]
　FIG. 1 shows an example of a reflective infrared spectroscopic analysis spectrum on the surface of the SiO 2 intermediate oxide film layer. The spectrum shown in FIG. 1 is an example of deconvolution of the SiO 2 peak assuming a Gauss distribution . At the time of deconvolution, the distribution function is set to one of Voigt, Gaussian, and Lorentz.
[0079]
　The peak intensity may be defined by the analysis software as the peak height after subtracting the background, or as the integrated intensity of the peak.
[0080]
　Si (Mn) O x When peak derived does not appear clearly, the deconvolution of the peaks due to the fitting, it is possible to extract the peak intensity.
[0081]
　The present inventors have found that the wave number 1250 cm -1 SiO of 2 peak intensity I from A and, wavenumber 1200 cm -1 Si (Mn) O of x peak intensity I B if it meets the following formula (1), good It was found that a good film adhesion can be obtained.
　I B / I A ≧ 0.010 · · · (1)
[0082]
　I B / I A is not defined limit, there is a limit to the amount of solid solution or thickening amount of Mn, Considering this limit, I B / I A limit is about 10. I B / I A is a point to reliably ensure good film adhesion, preferably 0.010 1-5. More preferably, it is 0.010 to 1.
[0083]
　When the element M (M: Mn, Al, B) is dissolved in the SiO 2 intermediate oxide film layer, the solid solution mode of the element M can be analyzed by the glow discharge emission analysis method (GDS). In that case, the relationship between the depth position of the SiO 2 intermediate oxide film layer and the depth position of the element M is important.
[0084]
The depth position of the 　SiO 2 intermediate oxide film layer can be analyzed from the Si-derived GDS spectrum (hereinafter, FSi (t)). This will be described below.
[0085]
　The GDS spectrum may be smoothed using peak analysis software. Further, from the viewpoint of improving the accuracy of peak analysis, the measurement time interval Δt is preferably small, preferably 0.05 seconds or less. Hereinafter, t represents a time (second) corresponding to the depth position of the sample.
[0086]
　t is a variable when the GDS spectrum is a function of time. When the SiO 2 intermediate oxide film layer is present on the surface of the sample collected from the steel plate, in the region corresponding to the surface of the sample, in the Si-derived GDS spectrum, (A) the peak rising position from the background and (B) the peak The apex position and (C) the peak end position to the background can be observed.
[0087]
　Here, the time t corresponding to the peak rising position is Ts, the time t corresponding to the peak apex is Tp, and the time t corresponding to the peak end position is Tf. The SiO 2 intermediate oxide film layer corresponds to the outermost surface of the measurement sample. That is, assuming that t of the measurement start point of the GDS spectrum corresponds to the peak rising position, the measurement start point of the GDS may be defined as Ts. Further, the peaks are symmetrical according to the normal distribution and can be defined as Tf = 2Tp-Ts.
[0088]
　Since the measurement time interval Δt of the GDS spectrum is as small as 0.05 seconds or less, Ts ≈ 0 may be approximated and Tf = 2 × Tp may be set. The method for determining Tp will be described below.
[0089]
　Tp corresponds to the peak apex position of the Si-derived GDS spectrum. To determine the peak apex position, F Si (t) is secondarily differentiated over time, and t corresponds to the minimum value of the second derivative curve ( see "d 2 F (t) / dt 2 " in FIG. 1 ). Just find. However, this minimum value is limited to those found in the range of t = 0 seconds or more and Δt × 100 seconds or less. This is because the SiO 2 intermediate oxide film layer exists only on the surface of the sample and does not exist inside the steel sheet, so that t has a relatively small value.
[0090]
　Further, in the curve f Si (t) (= dF Si (t) / dt) obtained by first -ordering F Si (t) with respect to time (see “dF (t) / dt” in FIG. 1), t = In the range of Ts to Tp, if f Si (t) ≧ 0, it is more decisive that Tp corresponds to the peak apex position.
[0091]
　The derivative of the differential curve may be obtained, or f (t n ) = [F (t n ) -F (t n-1 )] / [t n- t n-1 ] by the difference method . It may be obtained by approximating with. Here, the nth measurement point (time) is t n, and the spectral intensity at that time is F (t n ).
[0092]
　When the peak derived from Si is unclear, it can be analyzed from the GDS spectrum derived from Fe [hereinafter, F Fe (t)]. In this case, in the first-order differential curve of F Fe (t) (hereinafter referred to as f Fe (t)), when t corresponding to the maximum value is Tf, the Tp is Tp = 0.5. Although it is shown as × (Tf + Ts), it may be approximated to Ts≈0 and Tp = 0.5 × Tf. This is because the maximum value of f Fe (t) corresponds to the interface between SiO 2 and the base iron.
[0093]
　However, this maximum value is limited to those found in the range of t = 0 seconds or more and Δt × 100 seconds or less. This is because the SiO 2 intermediate oxide film layer exists only on the surface of the sample and does not exist inside the steel sheet, so that t has a relatively small value.
[0094]
　In the electromagnetic steel sheet of the present invention, for the purpose of improving the film adhesion, it is necessary to concentrate the element M such as Mn, Al, B at the position of t = Tp corresponding to the central portion of the SiO 2 intermediate oxide film layer. There is. However, it is impossible to keep the element M such as Mn, Al, and B at the position of t = Tp, and the element M is actually distributed over the range of t = Ts to Tp.
[0095]
　That, SiO 2 solid solution of the element M which is a solid solution in the intermediate oxide layer, GDS spectra from the element M (hereinafter, F M (t)) can be confirmed using. Specifically, the value when f M (t) is integrated in the integration range: t = Ts to Tp may satisfy the following equation (2).
[0096]
[Number 3]

[0097]
　Since a plurality of elements M such as Mn, Al, and B are present, at least one or two or more of the following formulas (3) to (5) may be satisfied.
[0098]
[Number 4]

[0099]
　Note that t in the GDS analysis is not continuous, and f M (t) is a collection of discontinuous points even when t = Ts to Tp . Therefore, each point of f M (t) is connected by a straight line and approximated as a continuous function for integration. It should be noted that the integrated value using Σ may be used.
[0100]
　Elements M such as Mn, Al, and B can also be detected by chemical analysis. The steel plate portion of the sample in the state before the tension insulating film is formed or the sample in the state where the tension insulating film is removed is dissolved by the iodine-methanol method to extract the SiO 2 intermediate oxide film layer. Next, the extracted SiO 2 intermediate oxide film layer is chemically analyzed using ICP or the like. As a result, the metal element M that has penetrated into the SiO 2 intermediate oxide film layer can be captured.
[0101]
The solid solution amount (or concentration amount) of the metal element M in the 　SiO 2 intermediate oxide film layer may be mass%, Mn and Al may be 0.01% or more, and B may be 0.001% or more. There is no particular upper limit, but Mn and Al are difficult to dissolve (concentrate) in excess of 0.5%, and B is difficult to dissolve (concentrate) in excess of 0.2%.
[0102]
　To verify the effect of improving film adhesion by reflective infrared spectroscopic analysis, GDS, chemical analysis, etc., the steel sheet is in a state after the SiO 2 intermediate oxide film layer is formed on the surface of the steel sheet and before the tension insulating film is formed. The sample is most suitable, but for steel sheet samples with a tension insulating film formed on the surface, only the tension insulating film is completely removed by pickling or ultrasonic cleaning with alcohol, water, etc. after alkaline cleaning. It may be removed and used for analysis.
[0103]
　Further, after pickling or ultrasonic cleaning with alcohol, water, etc., the surface of the steel sheet sample is further cleaned in an atmosphere of 100% hydrogen at 800 ° C. or higher and 1100 ° C. or lower for 1 hour or longer. Annealing for less than an hour may be performed for analysis. Since SiO 2 is a stable compound, SiO 2 is reduced by the above annealing, and the SiO 2 intermediate oxide film layer does not disappear.
[0104]
　
　The electromagnetic steel sheet of the present invention is hot-rolled, hot-rolled sheet annealed, cold-rolled, and primary recrystallized annealed onto continuously cast steel pieces melted in a converter in the same manner as ordinary electromagnetic steel sheets. , Secondary recrystallization annealing, annealing to form a SiO 2 intermediate oxide film layer, and annealing to form an insulating film.
[0105]
　The hot rolling may be direct hot rolling or continuous hot rolling, and the heating temperature of the steel piece is not limited. Cold rolling may be cold rolling or warm rolling twice or more, and the rolling reduction is not limited. The secondary recrystallization annealing may be either batch annealing in a box-shaped furnace or continuous line annealing, and does not depend on the annealing method.
[0106]
　The annealing separating agent may contain an oxide such as alumina, magnesia, or silica, and may be of any type.
[0107]
　When producing an excellent grain-oriented electrical steel sheet in film adhesion, SiO 2 in forming the intermediate oxide layer, SiO 2 generates the intermediate oxide layer, the metal element M is SiO, such as Mn 2 intermediate oxide layer It is important to adopt heat treatment conditions that dissolve or concentrate in. That is, it is important to select the temperature and time at which the metal element M can dissolve or concentrate in the SiO 2 intermediate oxide film layer.
[0108]
　In the electromagnetic steel sheet of the present invention, the SiO 2 intermediate oxide film layer is formed by annealing the steel sheet after secondary recrystallization at a temperature T1 (° C.) of 600 ° C. or higher and 1200 ° C. or lower.
[0109]
　If the annealing temperature is less than 600 ° C., SiO 2 is not formed and the SiO 2 intermediate oxide film layer is not formed. Therefore, the annealing temperature is set to 600 ° C. or higher. On the other hand, when the annealing temperature exceeds 1200 ° C., the formation reaction of the SiO 2 intermediate oxide film layer becomes non-uniform, the unevenness between the SiO 2 intermediate oxide film layer and the base steel sheet becomes severe, and the film adhesion deteriorates. Therefore, the annealing temperature is set to 1200 ° C. or lower. Preferably, it is 700 to 1100 ° C., which is the precipitation temperature of SiO 2 .
[0110]
　The annealing time is set to 5 seconds or more in order to grow the SiO 2 intermediate oxide film layer and secure the layer thickness necessary for ensuring excellent film adhesion. It is preferably 20 seconds or more. The annealing time may be long from the viewpoint of ensuring excellent film adhesion, but from the viewpoint of productivity, the upper limit is 200 seconds. It is preferably 100 seconds or less.
[0111]
　The annealing atmosphere is an annealing atmosphere that produces externally oxidized silica (SiO 2 intermediate oxide film layer) and avoids the formation of lower oxides such as firelite, wustite, and magnetite. Therefore, the ratio of water vapor pressure and hydrogen pressure of the annealing atmosphere
of oxygen partial pressure P H2 O / P H2 , and an oxygen partial pressure which satisfies the following equation (6). It is preferably 0.05 or less.
　P H2O / P H2 ≦ 0.15 · · · (6)
[0112]
　Oxygen partial pressure P H2 O / P H2 lower the external oxidation type silica (SiO 2 intermediate oxide layer) is easy to produce, but easy to exhibit the effect of the present invention, the oxygen partial pressure P H2 O / P H2 of 5 Since it is difficult to control it to less than 0.0 × 10 -4 , industrially, about 5.0 × 10 -4 is a practical lower limit.
[0113]
　In order to effectively dissolve (or concentrate) the metal element M such as Mn, Al, and B in the SiO 2 intermediate oxide film layer, it is necessary to secure a temperature at which the metal element M can diffuse. Therefore, in the cooling after annealing in which the SiO 2 intermediate oxide film layer is formed, T2 (° C.) or higher and T1 (° C.) defined by the following formula (7), which is the diffusion temperature range to the SiO 2 intermediate oxide film layer. The following temperature range is cooled at an average cooling rate of CR1 (° C./sec) of 50 ° C./sec or less.
[0114]
　Cooling of the average cooling rate CR1 of 50 ° C./sec or less does not deteriorate the characteristics of the electrical steel sheet of the present invention, but from the viewpoint of productivity, CR1 is preferably 0.1 ° C./sec or more. If the cooling rate is increased after cooling to T2 (° C.), thermal strain is introduced and the film adhesion and magnetic characteristics deteriorate. Therefore, the average cooling rate CR2 in the temperature range of 100 ° C. to T2 (° C.) is as follows. Let the average cooling rate satisfy the formula (8).
[0115]
　T2 (° C) = T1 (° C) -100 ... (7)
　CR1> CR2 ... (8)
[0116]
　The heating rate for heating the steel sheet is also important in forming the SiO 2 intermediate oxide film having excellent film adhesion . Oxides other than SiO 2 not only reduce the adhesion of the tension insulating film, but also hinder the surface smoothness of the steel sheet and cause deterioration of the iron loss characteristics. Therefore, the heating rate at which oxides other than SiO 2 are not generated as much as possible. Need to be adopted.
[0117]
　As described in Non-Patent Document 1, SiO 2 is not as stable as other Fe-based oxides, so it is preferable to adopt a thermal history in which Fe-based oxides are not generated during heating. Specifically, by setting the average heating rate HR1 in the temperature range from 100 ° C. to 600 ° C. to 10 ° C./sec or more, the formation of Fe X O can be avoided. The faster the heating rate in this temperature range, the more preferable, but for industrial reasons, the upper limit of the average heating rate HR1 is preferably 200 ° C./sec. Preferably, HR1 is 20 to 150 ° C./sec, more preferably 50 to 100 ° C./sec.
Example
[0118]
　Hereinafter, the technical contents of the present invention will be further described with reference to examples of the present invention. The conditions in the examples shown below are one condition example adopted for confirming the feasibility and effect of the present invention, and the present invention is not limited to this one condition example. Further, the present invention can adopt various conditions as long as the gist of the present invention is not deviated and the object of the present invention is achieved.
[0119]
　 After
　soaking the silicon steel having the composition shown in Table 1-1 at 1100 ° C. for 60 minutes, it is subjected to hot rolling to obtain a hot-rolled steel sheet having a thickness of 2.6 mm, and the hot-rolled steel sheet is 1100. It was annealed at ° C., pickled, and then cold-rolled once or cold-rolled a plurality of times with intermediate annealing in between to obtain a cold-rolled steel sheet with a final plate thickness of 0.23 mm.
[0120]
[Table 1-1]

[0121]
　A cold-rolled steel sheet having a final thickness of 0.23 mm was subjected to decarburization annealing and nitriding annealing. Then, a water slurry of an annealing separator mainly composed of alumina was applied, and finish annealing was performed at 1200 ° C. for 20 hours. Next, the finish annealing plate was subjected to oxygen partial pressure PH2O / PH2 : 0.12, annealing temperature T1: 1000 ° C., annealing time: 30 seconds, average heating rate HR1: 30 ° C. in a temperature range of 100 ° C. to 600 ° C. or lower. Annealing was performed under the condition of / sec to form a SiO 2 intermediate oxide film layer on the surface of the steel sheet .
[0122]
　The average cooling rate CR1 in the temperature range of T2 ° C. (800 ° C.) or higher and T1 ° C. (900 ° C.) or lower is 50 ° C./sec, and the average cooling rate CR2 is 100 ° C. or higher and lower than T2 ° C. (800 ° C.). Was 30 ° C./sec.
[0123]
　Then, a coating liquid for forming an insulating film was applied to the surface of the steel sheet and baked to form a tension insulating film. Table 1-2 shows the chemical composition of the base steel sheet of the manufactured grain-oriented electrical steel sheet. In addition, the film adhesion of the insulating film was evaluated, and the magnetic characteristics (magnetic flux density) were evaluated.
[0124]
[Table 1-2]

[0125]
　The film adhesion of the tension insulating film was evaluated by the film residual area ratio when the evaluation sample was wound around a cylinder having a diameter of 20 mm and bent by 180 °. The evaluation is VG (very excellent) when the film residual area ratio is 95% or more without peeling from the steel sheet, G (excellent) when 90% or more and less than 95%, and 80% or more and less than 90%. F (effective) and less than 80% were B (ineffective).
[0126]
　The magnetic properties were evaluated according to JIS C 2550. The magnetic flux density was evaluated using B8. B8 is a magnetic flux density at a magnetic field strength of 800 A / m, and serves as a criterion for determining the quality of secondary recrystallization. B8 = 1.89T or more was judged to be secondary recrystallization.
[0127]
　Incidentally, for some samples, SiO 2 after the formation of the intermediate oxide layer, without forming the tension insulating film, SiO 2 intermediate oxide layer and the thickness survey, SiO 2 of the degree of lattice matching intermediate oxide layer Used for investigation. The film thickness of the SiO 2 intermediate oxide film layer was identified by TEM observation according to the method described in Patent Document 25. The lattice consistency of the SiO 2 intermediate oxide film layer was investigated by reflective infrared spectroscopic analysis. Table 2 shows a series of evaluation results.
[0128]
[Table 2]

[0129]
　Symbols B1 to B13 are examples of inventions, and all of them have the effect of invention. None of the invention steels B1 to B6 contains a selective element. The evaluation was limited to "F" because S was out of the preferred range for the invention steel B1, Si was for B2 and B4, acid-soluble Al was for B3, and N was for B5. However, although the invention steel B6 did not contain a selective element, the evaluation was relatively good as "G". This is because in the invention steel B6, Si, Mn, acid-soluble Al, and N are all preferable or controlled in a more preferable range. The invention steels B7 to B13 contain any one of Cr, Cu, Sn, and B as a selective element. Since B7 to B12 contain one or two of Cr, Cu, Sn, and B as selective elements, a relatively good result of "G" was obtained. Since the invention steel B13 contains three types of Cr, Cu, and Sn, a particularly good result of "VG" was obtained.
[0130]
　On the other hand, symbols b1 to b7 are comparative examples. Since the comparative examples of symbols b3 to b5 contain a large amount of Si, Al, and N, respectively, they have poor brittleness at room temperature, and cold spreading itself is impossible. Therefore, in the comparative examples of the symbols b3 to b5, the adhesion was not evaluated.
[0131]
　In the comparative examples of symbols b1, b2, and b6, the content of the additive element was out of the scope of the present invention, so that none of them was recrystallized secondarily. The samples that did not undergo secondary recrystallization had poor film adhesion. If the secondary recrystallization was not performed, it is considered that the crystal grain size of the steel sheet was fine, the surface unevenness was severe, and the oxide layer was not formed appropriately. In the comparative steel b7, S was out of the upper limit of the present invention, and the SiO 2 intermediate oxide film layer was not preferably formed, so that the film adhesion was poor.
[0132]
　 After
　soaking the silicon steel having the composition shown in Table 1-1 at 1100 ° C. for 60 minutes, it is subjected to hot rolling to obtain a hot-rolled steel sheet having a thickness of 2.6 mm, and the hot-rolled steel sheet is 1100. It was annealed at ° C., pickled, and then cold-rolled once or cold-rolled a plurality of times with intermediate annealing sandwiched between them to obtain a cold-rolled steel sheet having a final plate thickness of 0.23 mm.
[0133]
　A cold-rolled steel sheet having a final thickness of 0.23 mm was subjected to decarburization annealing and nitriding annealing, and then a water slurry of an annealing separator mainly composed of alumina was applied and finish annealing was performed at 1200 ° C. for 20 hours. Next, the finish annealing plate was subjected to oxygen partial pressure PH2O / PH2 : 0.01, annealing temperature T1: 800 ° C., annealing time: 60 seconds, average heating rate HR1: 90 ° C. in a temperature range of 100 ° C. to 600 ° C. or lower. Annealing was performed under the condition of / sec to form a SiO 2 intermediate oxide film layer on the surface of the steel sheet .
[0134]
　The average cooling rate CR1 in the temperature range of T2 ° C. (700 ° C.) or higher and T1 ° C. (800 ° C.) or lower is 50 ° C./sec, and the average cooling rate CR2 is 100 ° C. or higher and lower than T2 ° C. (700 ° C.). Was 30 ° C./sec.
[0135]
　Then, a coating liquid for forming an insulating film was applied to the surface of the steel sheet and baked to form a tension insulating film, and the film adhesion of the insulating film was evaluated and the magnetic characteristics (magnetic flux density) were evaluated.
[0136]
　For some samples, SiO 2 after forming an intermediate oxide layer, without forming the tensioning insulating coating, SiO 2 film thickness of the intermediate oxide layer investigation and, SiO 2 lattice matching of the intermediate oxide layer And the solid solubility of Mn in the SiO 2 intermediate oxide film layer. The solid solubility of Mn was determined by GDS analysis.
[0137]
　Table 3, SiO 2 thickness of the intermediate oxide layer, SiO by reflection infrared spectroscopy 2 lattice matching degree of the intermediate oxide layer, Mn by GDS, Al and solid solubility of B, and, film adhesion The evaluation result of sex is shown. The measurement time of GDS was 100 seconds, and the time interval was 0.05 seconds. Both the measuring method and the evaluation method were carried out according to Example 1.
　The chemical composition of the base steel sheet of the manufactured grain-oriented electrical steel sheet is as shown in Table 1-2. When the equations (3) to (5) were satisfied, it was evaluated as "OK", and when it was not satisfied, it was evaluated as "NG".
[0138]
[Table 3]

[0139]
　Symbols C1 to C7 are examples of inventions, and it has been confirmed by reflective infrared spectroscopic analysis that a SiO 2 intermediate oxide film layer having excellent lattice consistency is formed in each of them.
　Since the invention steel C7 contains four kinds of selective elements Cr, Cu, Sn, and B, the evaluation "G" of the invention steels C1 to C6 which does not contain the selective elements or contains only one kind of the selective elements. In comparison with the above, "VG" having particularly good film adhesion is obtained.
[0140]
　 After
　soaking the silicon steel having the composition shown in Table 1-1 at 1100 ° C. for 60 minutes, it is subjected to hot rolling to obtain a hot-rolled steel sheet having a thickness of 2.6 mm, and the hot-rolled steel sheet is 1100. It was annealed at ° C., pickled, and then cold-rolled once or cold-rolled a plurality of times with intermediate annealing sandwiched between them to obtain a cold-rolled steel sheet having a final plate thickness of 0.23 mm.
[0141]
　A cold-rolled steel sheet having a final thickness of 0.23 mm was subjected to decarburization annealing and nitriding annealing. Then, a water slurry of an annealing separator mainly composed of alumina was applied, and finish annealing was performed at 1200 ° C. for 20 hours. Next, the finish annealed plate was annealed under the conditions shown in Tables 4-1 and 4-2 to form a SiO 2 intermediate oxide film layer on the surface of the steel sheet . Then, a coating liquid for forming an insulating film was applied to the surface of the steel sheet and baked to form a tension insulating film, and the adhesion of the insulating film was evaluated and the magnetic characteristics (magnetic flux density) were evaluated.
　The chemical composition of the base steel sheet of the manufactured grain-oriented electrical steel sheet is as shown in Table 1-2.
[0142]
　Table 4-1 and Table 4-2, SiO 2 thickness of the intermediate oxide layer, SiO by reflection infrared spectroscopy 2 shows the degree of lattice matching intermediate oxide layer, and the evaluation results of film adhesion. Both the measuring method and the evaluation method were carried out according to Example 1.
[0143]
[Table 4-1]

[0144]
[Table 4-2]

[0145]
　Symbols D1 to D27 are examples of the invention, and all of them can enjoy the effects of the present invention.
　Regarding the invention steels D1 to D9, since the annealing temperature, annealing time, heating rate HR1 and oxygen partial pressure of the invention steels D1 to D3 were controlled outside the preferable ranges, the evaluation was limited to "F", but the invention steel D4 In ~ D6, the annealing temperature, annealing time, heating rate HR1, and oxygen partial pressure were all controlled within preferable ranges, so that the results were good as “G”.
　In the steels G7 to G9 of the invention, the annealing temperature, annealing time, and oxygen partial pressure are all controlled in a preferable range, and the temperature rising rate HR1 is controlled in a more preferable range. Therefore, "G" having good film adhesion was obtained.
　Although the annealing temperature, annealing time, heating rate HR1, and oxygen partial pressure were outside the preferable ranges of the invented steels D10 to D13, they contained Cr and Sn as selective elements, and thus had relatively good film adhesion. "G" was obtained.
　The invented steels D14 to D15 have relatively good film adhesion because the annealing temperature, annealing time, heating rate HR1, and oxygen partial pressure are controlled in preferable ranges and contain Cr and Sn as selective elements. A certain "G" was obtained.
　The invented steels D16 to D18 are controlled in the annealing temperature, annealing time, and oxygen partial pressure in a preferable range, contain Cr and Sn as selective elements, and the heating rate HR1 is controlled in a more preferable range. Therefore, "VG" having particularly good film adhesion was obtained.
　Further, the invented steels D19 to D21 are also relatively good because they contain Cr, Cu and Sn as selective elements, although the annealing temperature, annealing time, heating rate HR1 and oxygen partial pressure were outside the preferable ranges. “G”, ​​which has good film adhesion, was obtained. Since the annealing temperature, annealing time, and oxygen partial pressure of the invented steels D22 to D27 are all controlled within preferable ranges, "VG" having particularly good film adhesion was obtained.
[0146]
　On the other hand, the symbols d1 to d9 are comparative examples. In the comparative examples of the symbols d1 to d3 and d5, since any of the annealing temperature, annealing time, and oxygen partial pressure at the time of forming the SiO 2 intermediate oxide film layer is outside the range of the present invention, SiO 2 is used. Since the intermediate oxide film layer was not formed, it could not be evaluated by reflective infrared spectroscopic analysis.
[0147]
　For a comparison example of symbol d4, d8, d9, SiO 2 for the cooling rate of the intermediate oxide layer is outside the range of the present invention, SiO 2 poor lattice matching degree of the intermediate oxide layer, the evaluation of film adhesion Was "B".
　In d6, HR1 was above the upper limit, and in d7, HR1 was less than the lower limit, so that a large amount of Fe-based oxide was formed. Therefore, the evaluation of film adhesion was B.
Industrial applicability
[0148]
　As described above, according to the present invention, the formation of a glass film is intentionally suppressed, the glass film is removed by means such as grinding or pickling, and the surface of the steel sheet is flattened until it has a mirror gloss. A tension-applying insulating film having excellent film adhesion can be formed on the surface of the finish-annealed unidirectional silicon steel sheet without impairing the magnetic properties and its stability. Therefore, the present invention is highly applicable in the electromagnetic steel sheet manufacturing industry and the electromagnetic steel sheet utilization industry.
The scope of the claims
[Claim 1]
　With the base steel plate; with the intermediate oxide film layer
　formed on the base material steel plate , containing SiO 2 and having an average film thickness of 1.0 nm to 1.0 μm;
　the tension formed on the intermediate oxide film layer. The 　base metal steel plate has an insulating film and;
as
a chemical component, C: 0.010% or less, Si: 2.50 to 4.00%, acid-soluble Al: 0.010% or less in mass%. N: 0.012% or less, Mn: 1.00% or less, S: 0.020% or less, the
　balance is
　composed of Fe and impurities, and by reflective infrared spectroscopic analysis of the surface of the intermediate oxide film layer. , 1250 cm -1 peak intensity I a and, 1200 cm -1 peak intensity I B satisfies the following formula (1)
oriented electrical steel sheet, characterized in that.
　I B / I A ≧ 0.010 · · · (1)
[Claim 2]
　The grain-oriented electrical steel sheet according to claim 1, wherein the base metal steel sheet further contains B: 0.001 to 0.010% in mass% as the chemical component.
[Claim 3]
　Characterized in that said base material steel plate, as the chemical components, by
　　mass%,
　　Sn: 0.01 ~ 0.20%;
　　Cr: 0.01 ~ 0.50%; Cu: 0.01 ~ 0.50%;
1 The directional electromagnetic steel sheet according to claim 1 or 2, further containing seeds or two or more kinds.
[Claim 4]
A claim characterized in that 　the time derivative curve f M (t) of the glow discharge emission analysis spectrum of the element M (M: Mn, Al, B) on the surface of the intermediate oxide film layer satisfies the following formula (2). Item 2. The directional electromagnetic steel plate according to any one of Items 1 to 3.
[

　　Equation 1] Tp: Time t (seconds) corresponding to the minimum value of the second-order time derivative curve of the glow discharge emission analysis spectrum of
　　Si Ts: Time t (seconds) corresponding to the start point of glow discharge emission analysis of Si
[Claim 5]
　The method for producing a directional electromagnetic steel plate according to any one of claims 1 to 4, wherein the method has
　an oxide film forming step of forming an intermediate oxide film layer on the surface of the steel plate, and the
　oxide film forming step includes an oxide film forming step. ,
　　Annealing temperature T1: 600-1200 ° C. Annealing time: 5-200 seconds, oxygen partial pressure PH2O / PH2 : 0.15 or less, average heating rate in the temperature range of 100 ° C. to 600 ° C. HR 1:10-200 ° C. annealed at conditions was carried out;
　　after the annealing, the average cooling rate CR1 of the temperature range of T2 ° C. ~ T1 ° C. and 50 ° C. / sec or less, and less than a 100 ° C. or higher T2 ° C. lower than the temperature range average cooling rate CR2 of CR1 A
method for manufacturing a directional electromagnetic steel plate, which is characterized by the above.
　　Here, T2 ° C represents the temperature represented by T1 ° C-100.