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 5 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. In addition to ensuring insulation, it is effective in reducing iron loss.
[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 grain-oriented electrical steel sheets.
[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 secure the film tension sufficient to bring out the effect of mirroring and also 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 References 7-10.
[0012]
　For example, the technique disclosed in Patent Document 8 is that a unidirectional silicon steel sheet that has been finish-annealed and prepared to be mirror-finished or close to a mirror surface is annealed at a specific atmosphere at each temperature to surface the steel sheet. This is a method of forming an external oxide type oxide film on the steel sheet and ensuring the adhesion between the tension insulating film and the steel sheet by the oxide film.
[0013]
　The technique disclosed in Patent Document 9 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 steel sheet oxidation that occurs when forming a crystalline tension insulating film.
[0014]
　The technique disclosed in Patent Document 10 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 10 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. 07-278670
Patent Document 2: Japanese Patent Application Laid-Open No. 11-106827
Patent Document 3: Japanese Patent Application Laid-Open No. 11-118750
Patent Document 4: Japanese Patent Application Laid-Open No. 11-118750 JP
Patent Document 5: Japanese Patent 2003-268450 JP
Patent Document 6: Japanese Sho 48-039338 Patent Publication
Patent Document 7: Japanese Sho 60-131976 Patent Publication
Patent Document 8: Japanese Patent Kaihei 06-184762
Patent Document 9: Japanese Patent Application Laid-Open No. 07-278833
Patent Document 10: Japanese Patent Application Laid-Open No. 2002-3486343
Non-patent literature
[0016]
Non-Patent Document 1: Iron and Steel, vol 99 (2013), 40.
Outline of the invention
Problems to be solved by the invention
[0017]
　In a unidirectional silicon 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. When the formation of steel sheet is intentionally suppressed, the glass film is removed by means such as grinding 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 problem 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.
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. 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, an oxide of the intermediate oxide layer, Si oxide (SiO 2 are), SiO 2 in the intermediate oxide layer, also, SiO 2 at the interface of the intermediate oxide layer and the steel plate, Al, Cu, Cr, It was found that one type or two or more types of Ca were concentrated.
[0021]
　When Al, Cr, Cu, and Ca are concentrated at the interface between the SiO 2 intermediate oxide film layer and the steel sheet, attractive electron-electron interaction occurs at the interface, and the steel sheet and the SiO 2 intermediate oxide film layer adhere to each other. It is considered that the sex has improved.
[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: 0.01% or less, Si: 2.50 to 4.00%, acid-soluble Al: 0.0010 to 0.0100%, N: 0. It contains 012% or less, Mn: 1.00% or less, S: 0.02% or less, and the balance is composed of Fe and impurities.
　The time derivative curve f M (t) of the glow discharge emission analysis spectrum of the metal element M (M: Al) of the SiO 2 intermediate oxide film layer satisfies the following formula (1).
[0024]
[Number 1]

[0025]
　　T p : Time t (seconds) corresponding to the minimum value of the second-order time differential curve of the glow discharge emission analysis spectrum of Si
　　T f : 2 T p −T with the analysis start point of the glow discharge emission analysis spectrum of Si as T s. Time t (seconds) corresponding to s
[0026]
　(2) In the directional electromagnetic steel plate according to (1) above, the base steel plate has Cr: 0.01 to 0.50% and Cu: 0.01 to 0% in terms of mass% as the chemical components. Glow discharge emission analysis spectrum of the metal element M (M: Cr, Cu, Ca) of the SiO 2 intermediate oxide film layer further containing one or more of 50% and Ca: 0.001 to 0.05%. The time differential curve f M (t) of the above may satisfy one or more of the following equations (2) to (4).
[0027]
[Number 2]

[0028]
　(3) In the grain-oriented electrical steel sheet according to (1) or (2) above, the base steel sheet has Sn: 0.01 to 0.20%, B: 0. It may further contain one or two of 001 to 0.010%.
[0029]
　(4) The method for manufacturing a grain-oriented electrical steel sheet according to another aspect of the present invention is the method for manufacturing a grain-oriented electrical steel sheet according to any one of (1) to (3) above. 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 1200 seconds, the oxygen partial pressure PH2O / PH2 : 0.15 or less, and the average heating rate in the temperature range of 600 ° C. to T1 ° C. HR2: Annealing is performed under the condition of 5 to 50 ° C./sec, and after the 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 temperature range of 100 ° C. or more and less than T2 ° C. The average cooling rate CR2 is set to less than CR1. Here, T2 ° C represents a temperature represented by T1 ° C-100 ° C.
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 insulating film having excellent film adhesion can be formed on the surface of the grain-oriented electrical steel sheet without impairing its magnetic properties and its stability.
A brief description of the drawing
[0031]
FIG. 1 is a diagram showing a differential curve of a spectrum derived from Si obtained by glow discharge emission analysis (GDS).
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 metal steel sheet has a chemical composition of
　　C: 0.010% or less;
　　Si: 2.50 to 4.00%;
　　acid-soluble Al: 0.0010 to 0.0100% or less;
　　N: 0. .012% or less;
　　Mn: 1.00% or less;
　　S: 0.02% or less;
the balance is composed of Fe and impurities, and the glow discharge of the metal element M (M: Al) of the intermediate oxide film layer The time differential curve fM (t) of the emission analysis spectrum satisfies the following equation (1).
[0033]
[Number 3]

[0034]
　　T p : Si glow discharge emission spectrometry upstairs time period corresponding to the minimum value of the derivative curve t (in
　　seconds) T f : the analysis start point of the glow discharge optical emission spectrometry of Si T s as, 2T p - Time t (seconds) corresponding to T s
[0035]
　Further, the electromagnetic steel plate of the present invention is one or two of Cr: 0.01 to 0.50%, Cu: 0.01 to 0.50%, and Ca: 0.001 to 0.05% in terms of mass%. The time differential curves f M (t) of the glow discharge emission analysis spectrum of the metal element M (M: Cr, Cu, Ca) of the SiO 2 intermediate oxide film layer containing seeds or more are represented by the following formulas (2) to (t). One or two or more of 4) may be satisfied.
[0036]
[Number 4]

[0037]
　Further, the electromagnetic steel sheet of the present invention may further contain one or two kinds of Sn: 0.01 to 0.20% and B: 0.001 to 0.010% in mass%.
[0038]
　The method for manufacturing 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 Annealing temperature T1: 600-1200 ° C. Annealing time: 5-1200 seconds, oxygen partial pressure PH2O / PH2 : 0.15 or less, average heating rate in the temperature range of 600 ° C. to T1 ° C. HR2: 5-50 ° C. Annealing is performed under the condition of / sec, and after the 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 CR1. Less than. Here, T2 ° C represents a temperature represented by T1 ° C-100 ° C.
[0039]
　Hereinafter, the electromagnetic steel sheet of the present invention and the manufacturing method of the present invention will be described.
[0040]
　[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%.
[0041]
　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.
[0042]
　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.
[0043]
　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.
[0044]
　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.
[0045]
　Acid-soluble Al: 0.0010% or more, 0.0100% or less In the
　electromagnetic steel sheet of the present invention, acid-soluble Al (sol.Al) is an essential element from the viewpoint of improving film adhesion. That is, acid-soluble Al is an element that is concentrated at the interface between the SiO 2 intermediate oxide film layer and the steel sheet to form a concentrated layer, and the film adhesion is remarkably improved.
[0046]
　If the acid-soluble Al is less than 0.0010%, the concentrated layer is not formed, so the acid-soluble Al is 0.0010% or more. It is preferably 0.0030% or more.
[0047]
　On the other hand, the acid-soluble Al is contained in the slab composition 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 0.0100% 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.
[0048]
　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.
[0049]
　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.
[0050]
　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.
[0051]
　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.
[0052]
　S: 0.02% or less When
　S exceeds 0.02%, 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 0.02% or less. It is preferably 0.01% or less.
[0053]
　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.
[0054]
　Further, a part of S may be replaced with Se or Sb. In that case, a value converted by Seq = S + 0.406Se or Seq = S + 0.406Sb is used.
[0055]
　In addition to the above elements, the electrical steel sheet of the present invention may contain one or more of the following elements in order to improve the characteristics of the electrical steel sheet of the present invention.
[0056]
　Cr: 0.01 to 0.50%
　Cr is an element that is concentrated at the interface between the SiO 2 intermediate oxide film layer and the steel sheet to form a concentrated layer, which 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 combine with Si and O and inhibit the formation of the SiO 2 intermediate oxide 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 Al and Cr, is concentrated at the interface between the SiO 2 intermediate oxide film layer and the steel sheet to form a concentrated layer, which contributes to the improvement of film adhesion. Is. 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]
　Ca: 0.001 to 0.05%
　Like Al, Cr, and Cu, Ca is concentrated at the interface between the SiO 2 intermediate oxide film layer and the steel sheet to form a concentrated layer, which contributes to the improvement of film adhesion. It is an element to be used. If it is less than 0.001%, the effect of improving the film adhesion cannot be sufficiently obtained, so Ca is set to 0.001% or more. It is preferably 0.005% or more, more preferably 0.010 or more.
[0061]
　On the other hand, if it exceeds 0.05%, fine CaS is generated in the steel and the magnetic characteristics deteriorate, so the Ca is set to 0.05% or less. It is preferably 0.04% or less, more preferably 0.03% or less.
[0062]
　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 after secondary recrystallization, it was found that the smoothness of the steel sheet was improved. It is considered that this contributes to the formation of the interface between the SiO 2 intermediate oxide film layer and the steel sheet , which has few unevenness defects .
[0063]
　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.
[0064]
　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.
[0065]
　B: 0.001 to 0.010%
　B is concentrated at the interface between the SiO 2 intermediate oxide film layer and the steel sheet to form a concentrated layer, similarly to Al, Cr, Cu, and Ca (the present inventors). , The concentrated layer was confirmed by GDS), which is an element that contributes to the improvement of film adhesion. 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.
[0066]
　On the other hand, if it exceeds 0.010%, the strength of the steel sheet increases and the passability in cold rolling deteriorates, so B is set to 0.010% or less. It is preferably 0.008% or less, more preferably 0.006% or less.
[0067]
　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, Sn, Bi, Sb, Ag, Te, Ce, V, Co, Ni, Se, Re, Os, Nb, Zr, for the purpose of improving productivity by using scraps, etc. One or more of Hf, Ta, Pb, 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.
[0068]
　[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 grinding, pickling, or the like, 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 .
[0069]
Average film thickness of the 　SiO 2 intermediate oxide film layer: 1.0 nm or more and 1.0 μm or less If the average film thickness of the
　SiO 2 intermediate oxide film layer is less than 1.0 nm, sufficient film adhesion cannot be 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.
[0070]
　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.
[0071]
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).
[0072]
　The fact that the oxide constituting the intermediate oxide film layer is "SiO 2 " can be confirmed by elemental analysis by TEM or energy dispersive spectroscopy (EDS) associated with SEM. Since the chemical bond ratio of Si and O is not always 2, the characteristics of the electromagnetic steel sheet of the present invention are impaired even if the ratio is SiOx (x is an arbitrary number) as a result of analysis of the stoichiometric ratio. I can't.
[0073]
　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.
[0074]
　However, since the EDS spectrum of Si may include a spectrum derived from Si in the steel sheet, to be precise, the cross section of the steel sheet is analyzed with an electron probe microanalyzer (EPMA), and whether Si is derived from the steel sheet. , SiO 2 It is determined whether it is derived from the intermediate oxide film layer.
[0075]
　Further, SiO 2 intermediate oxide layer was measured with a Fourier transform infrared spectrophotometer (FT-IR), the wave number 1250 cm -1 SiO to 2 to ensure that the peak attributable exists, SiO 2 intermediate oxide layer It is preferable for identifying the compound constituting the layer.
[0076]
　However, since FT-IR is a method for selectively analyzing the compound on the outermost surface of the sample, the analysis is performed on (a) a sample in which a tension insulating film does not exist, or (b) tension insulation on the surface of a steel sheet. For samples with a film, perform this after completely removing the tension insulating film by alkaline cleaning or the like.
[0077]
　Infrared spectroscopy (IR) includes a reflection method and an absorption method. In the absorption method, information on the outermost surface of the sample and information on the inside of the steel plate are superimposed, so that the compound constituting the SiO 2 intermediate oxide film layer is formed. The reflection method is preferred for identifying.
[0078]
　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 . However, it is not sufficient to secure the film adhesion only by controlling the average film thickness of the SiO 2 intermediate oxide film layer to 1.0 nm or more and 1.0 μm or less.
[0079]
　SiO 2 by controlling the thickness of the intermediate oxide layer, the tension insulating film and SiO 2 can be ensured adhesion between the intermediate oxide layer (the film adhesion). However, the interface between the SiO 2 intermediate oxide film layer and the steel plate is the interface between the metal and the oxide, that is, the interface between different atoms, and the interface between the atoms is weak. Therefore, peeling often occurs starting from the interface between the SiO 2 intermediate oxide film layer and the steel sheet.
[0080]
　Therefore, Al is SiO 2 when concentrated in the interface between the intermediate oxide layer and the steel plate, SiO 2 electron interaction as attractive force between the intermediate oxide layer and the steel plate acts is believed that improved film adhesion. For example, since the interaction between C and Fe is attractive, it is known that when C segregates at the grain boundaries, the grain boundary strength increases. On the premise of this, in the electromagnetic steel sheet of the present invention, it can be considered that Al also caused an attractive electron-electron interaction between SiO 2 and Fe.
[0081]
　Although it is difficult to directly detect the degree of electron-electron interaction by experiment , the concentration mode of Al concentrated at the interface between the SiO 2 intermediate oxide film layer and the steel sheet exposes the SiO 2 intermediate oxide film layer. It is possible to analyze the surface of the steel sheet in the state of being made by the glow discharge emission analysis method (GDS).
[0082]
　In the electromagnetic steel sheet of the present invention , Al is concentrated at the interface between the SiO 2 intermediate oxide film layer and the steel sheet to form a concentrated layer. Therefore, the relationship between the depth position of the SiO 2 intermediate oxide film layer and the depth position of the Al concentrated layer is important. The existing position of the SiO 2 intermediate oxide film layer can be analyzed from the GDS spectrum derived from Si (hereinafter, may be referred to as “ FSi (t)”).
[0083]
　In the analysis, the obtained spectrum may be smoothed by using peak analysis software or the like. 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.
[0084]
　Hereinafter, t is a time (second) corresponding to the depth position of the sample, and is a variable when the GDS spectrum is used as a function of time.
[0085]
　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.
[0086]
　Here, t corresponding to the peak rising position is T s , t corresponding to the peak apex position is T p , and t corresponding to the peak end position is T f . The SiO 2 intermediate oxide film layer corresponds to the outermost surface of the measurement sample. That, t of the measurement starting point of the GDS spectra, as corresponding to a peak rising position, the measurement starting point of the GDS T s may be defined as. Further, the peaks are symmetrical according to the normal distribution and can be defined as T f = 2 T p − T s .
[0087]
　Since the measurement time interval Δt of the GDS spectrum is as small as 0.05 seconds or less, it may be approximated to T s ≈ 0 and T f = 2 × T p . In any case, in determining T f , it is necessary to determine T p . Hereinafter, T p is described a method of determining the.
[0088]
　FIG. 1 shows the differential curve of the spectrum derived from Si obtained by the glow discharge emission analysis method (GDS).
[0089]
　T p 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 sample surface 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-order differentiating F Si (t) with respect to time (see “dF (t) / dt” in FIG. 1), t = It is more decisive that T p corresponds to the peak apex position if f Si (t) ≥ 0 at all times in the range T s to T p .
[0091]
　The derivative may be obtained as the method for deriving the differential curve, or f (t n ) = [F (t n ) -F (t n-1 )] / [t n- t n- " by the difference method. 1 ] may be approximated. 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 T f , the T p is T p =. Although it is shown as 0.5 × (T f + T s ), it may be approximated to T s ≈ 0 and T p = 0.5 × T f . 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, Al needs to be concentrated at t = T f , which is the position of the interface between the SiO 2 intermediate oxide film layer and the steel sheet , for the purpose of improving the film adhesion . However, it is impossible to keep Al only at the position of t = T f , and in reality, it is distributed over the range of t = T p to T f starting from t = T f. Become. This region is hereinafter referred to as an interfacial concentrated layer.
[0095]
　In addition to Al, it has been confirmed that Cr, Cu, and Ca also contribute to the improvement of film adhesion by forming an interface-concentrated layer. That is, in the electromagnetic steel sheet of the present invention , the metal element M (M = Al, Cr, Cu, Ca) is interfacially concentrated in the range of t = T p to T f corresponding to the interface between the SiO 2 intermediate oxide film layer and the steel sheet. It forms a chemical layer.
[0096]
　The presence of the interface concentrated layer is, GDS spectra derived from the metal element M (hereinafter "F M can be confirmed using a may be referred to as (t)".). Specifically, F M time derivative curve f of (t) M integrating (t) (the integral range: t = T p ~ T f ) the time, if the integrated value is greater than 0, the metal element M include surfactants It can be determined that it exists as a concentrated layer.
[0097]
　Since the metal element M is uniformly distributed inside the steel sheet , the integrated value of f M (t) inside the steel sheet is 0 or a value as close to 0 as possible.
[0098]
　Further, t in the measurement of GDS is not continuous , and f M (t) is a collection of discontinuous points at t = T p to T f . 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.
[0099]
　From the above discussion, it is necessary to satisfy the following formula (1) in order for Al to be concentrated at the interface between the SiO 2 intermediate oxide film layer and the steel sheet and to exist as a concentrated layer.
[0100]
[Number 5]

[0101]
　Further, by satisfying one or more of the following formulas (2) to (4), the film adhesion is further improved.
[0102]
[Number 6]

[0103]
　In the electromagnetic steel sheet of the present invention, the metal element M (Al, Cr, Cu, Ca) 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 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. Thereby, the metal element M contained in the SiO 2 intermediate oxide film layer can be captured.
[0104]
　The metal element M (Al, Cr, Cu, Ca) may be present in the SiO 2 intermediate oxide film layer in a mass% of 0.05% or more and 2.00% or less in total. If it is less than 0.05%, the film adhesion is not improved, so that the total of the metal elements M is preferably 0.05% or more. More preferably, it is 0.10% or more.
[0105]
　On the other hand, if it exceeds 2.00%, the crystal lattice of SiO 2 is disturbed due to the influence of segregation , many lattice defects are introduced at the interface between the SiO 2 intermediate oxide film layer and the steel sheet, and the film adhesion deteriorates. The total of the metal elements M is preferably 2.00% or less. More preferably, it is 1.50% or less.
[0106]
　For verification of the effect of improving film adhesion by GDS or chemical analysis, the steel sheet sample in the state after forming the SiO 2 intermediate oxide film layer on the steel sheet surface and before forming the tension insulating film is the most suitable. For steel sheet samples with a tension insulating film formed on the surface, only the tension insulating film should be completely removed by pickling or ultrasonic cleaning with alcohol, water, etc. after alkaline cleaning before analysis. Just do it.
[0107]
　In addition, after pickling or ultrasonic cleaning with alcohol, water, etc., annealing at 800 ° C. or higher and 1100 ° C. or lower for 1 hour or more and 5 hours or less in an atmosphere of 100% hydrogen for the purpose of further surface cleaning. It may be carried out and subjected to analysis. Since SiO 2 is a stable compound, the SiO 2 is reduced by the above annealing, and the SiO 2 intermediate oxide film layer does not disappear.
[0108]
　The electromagnetic steel sheet of the present invention is hot-rolled, hot-rolled sheet annealed, cold-rolled, primary recrystallized annealed, and secondly formed by melting and continuously casting steel pieces in a converter in the same manner as in the production of ordinary electromagnetic steel sheets. It is manufactured by subjecting it to subsequent recrystallization annealing, annealing to form a SiO 2 intermediate oxide film layer, and annealing to form an insulating film.
[0109]
　The hot rolling may be direct hot rolling or continuous hot rolling, and the heating temperature of the steel piece is not limited. The 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.
[0110]
　The annealing separator may be any one containing an oxide such as alumina, magnesia, or silica, and it does not depend on the type.
[0111]
　In the case of producing a directional electromagnetic steel plate, when the SiO 2 intermediate oxide film layer is formed, the SiO 2 intermediate oxide film layer is formed, and the metal elements M (Al, Cr, Cu, Ca) are added to the SiO 2 intermediate oxide film layer. It is important to adopt heat treatment conditions that thicken the interface between the steel plate and the steel plate. That is, it is important to secure a concentration time at which Al, Cr, Cu, and Ca are concentrated at the interface between the SiO 2 intermediate oxide film layer and the steel sheet.
[0112]
　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 for 5 to 1200 seconds.
[0113]
　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 .
[0114]
　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.
[0115]
　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 oxygen partial pressure P which is the ratio of water vapor pressure and hydrogen pressure of the annealing atmosphere H2 O / P H2 , and an oxygen partial pressure which satisfies the following equation (5). It is preferably 0.05 or less.
　P H2O / P H2 ≦ 0.15 · · · (5)
[0116]
　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.
[0117]
　In order to effectively concentrate the metal element M (Al, Cr, Cu, Ca) at the interface between the SiO 2 intermediate oxide film layer and the steel sheet, it is necessary to secure the segregation temperature of the metal element M. Therefore, in cooling after annealing to form the SiO 2 intermediate oxide film layer, the temperature range of T2 (° C.) or higher and T1 (° C.) or lower defined by the following formula (6), which is the segregation temperature range, is set to 50 ° C. Cool at an average cooling rate of / sec or less. This average cooling rate is called CR1 (° C./sec).
[0118]
　Cooling at an average cooling rate of CR1 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 (7).
　T2 = T1-100 ・ ・ ・ (6)
　CR1> CR2 ・ ・ ・ (7)
[0119]
　In the formation of the SiO 2 intermediate oxide film, the heating rate for heating the steel sheet during annealing is also important. 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, heating in which oxides other than SiO 2 are not generated as much as possible. You need to adopt speed.
[0120]
The formation temperature range of 　SiO 2 is 600 ° C. or higher and T1 ° C. or lower. Therefore, in order to generate more SiO 2 , the average heating rate HR2 in this temperature range is set to 50 ° C./sec or less. However, if the heating rate is slow, Fe 2 SiO 4, which is more thermally stable than SiO 2 , is produced, so the average heating rate HR2 is set to 5 ° C./sec or more. Preferably, HR2 is 10-40 ° C / sec, more preferably 15-30 ° C / sec.
Example
[0121]
　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.
[0122]
　 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.
[0123]
[Table 1-1]

[0124]
　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 : 0.06, annealing temperature T1: 1000 ° C., annealing time: 30 seconds, average heating rate HR2: 30 ° C./in the temperature range of 600 ° C. to T1 ° C. Annealing was carried out under the condition of seconds to form a SiO 2 intermediate oxide film layer on the surface of the steel sheet .
[0125]
　The average cooling rate CR1 in the temperature range of T2 ° C. (900 ° C.) or higher and T1 ° C. (1000 ° C.) or lower is 40 ° C./sec, and the average cooling rate CR2 is 100 ° C. or higher and lower than T2 ° C. (900 ° C.). Was 5 ° C./sec.
[0126]
　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.
[0127]
[Table 1-2]

[0128]
　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 remaining 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).
[0129]
　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.
[0130]
　For some samples, after the SiO 2 intermediate oxide film layer was formed, the tension insulating film was not formed, and the film was used for the film thickness investigation of the SiO 2 intermediate oxide film layer and the investigation of the interface-concentrating element. The film thickness of the SiO 2 intermediate oxide film layer was identified by TEM observation according to the method described in Patent Document 10. Interfacial enrichment elements were investigated by GDS. The measurement time of GDS was 100 seconds, and the time interval was 0.05 seconds. Table 2 shows a series of evaluation results. When the formula (1) was satisfied, it was evaluated as "OK", and when it was not satisfied, it was evaluated as "NG".
[0131]
[Table 2]

[0132]
　B1 to B14 are examples of the invention, and all of them show good film adhesion, but B1 is out of the preferable range of S content, B2 is out of the preferable range of N content, and B3 and The Mn content of B14 is out of the preferable range. .. Further, the invention steels B10 and B11 have a Si content outside the preferable range, and the invention steels B12 and B13 have an acid-soluble Al content outside the preferable range.
　On the other hand, although B4 does not contain any selective element, all the elements are controlled to a preferable range or a more preferable range. Good film adhesion is obtained. B5 to B7 were also evaluated as "G" because they contained one or more of the selective elements Cr, Cu, Ca, Sn, and B. Since B8 and B9 contain 5 kinds of selective elements Cr, Cu, Ca, Sn, and B, the film adhesion is particularly good, and the evaluation is "VG".
　On the other hand, b1 to b8 are comparative examples. In b3, b5, and b6, steel a3, steel a5, and steel a6 each contained a large amount of Si, acid-soluble Al, and N, so that embrittlement at room temperature was remarkable and cold spreading was impossible. .. Therefore, none of b3, b5, and b6 has reached the evaluation of film adhesion.
[0133]
　The Si content of b2 was outside the range of the present invention, and the Mn content of b7 was outside the range of the present invention. Therefore, b2 and b7 did not recrystallize 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 SiO 2 intermediate oxide film layer could not be properly grown. The evaluation of b1 was "B" because C did not recrystallize secondarily due to the excessive presence of C, and C inhibited the formation of the Al interface-concentrated layer, which is advantageous for film adhesion. Since the acid-soluble Al content of b4 did not meet the range of the present invention, an interfacial concentrated layer was not formed, and the evaluation was also "B". The evaluation of b8 was "B" because S contained in excess inhibited the formation of the Al interface concentrated layer, which is advantageous for film adhesion.
[0134]
　 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.
[0135]
　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 : 0.005, annealing temperature: 800 ° C., annealing time: 60 seconds, average heating rate in the temperature range of 600 ° C. to T1 ° C. HR2: 20 ° C./sec. Annealed under the conditions of (1) to form a SiO 2 intermediate oxide film layer on the surface of the steel sheet .
[0136]
　The average cooling rate CR1 in the temperature range of T2 ° C. (900 ° C.) or higher and 1100 ° C. or lower is 20 ° C./sec, and the average cooling rate CR2 of 100 ° C. or higher and lower than T2 ° C. (900 ° C.) is 10 ° C./sec. It was set to seconds.
[0137]
　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.
[0138]
　Table 3 shows the evaluation results of the film thickness of the SiO 2 intermediate oxide film layer, the degree of concentration of the interface-concentrating element by GDS analysis, and the film adhesion. The measurement and evaluation were carried out according to the measurement and evaluation of Example 1. In addition, in the column of "Concentrating elements at the interface between the SiO 2 intermediate oxide film layer / steel sheet " in Table 3, the elements whose concentration was confirmed by the GDS spectrum were described. When the equations (1) to (4) were satisfied, it was evaluated as "OK", and when it was not satisfied, it was evaluated as "NG".
　The chemical composition of the base steel sheet of the manufactured grain-oriented electrical steel sheet is as shown in Table 1-2.
[0139]
[Table 3]

[0140]
　C1 to C7 are examples of the invention. The invention steels C1 to C5 contain at least one of Cr, Ca, Cu, and Sn as a selective element. Therefore, in the invented steels C1 to C5, concentration (segregation) of any one or more of Cr, Cu, Ca, and Sn was confirmed, and "G" having good film adhesion was obtained. The invented steels C6 and C7 contain the selective elements Cr, Ca, Cu, Sn and B. Concentration of Cr, Cu, and Ca was confirmed, and "VG", which is an evaluation result of better film adhesion than C1 to C5, was obtained.
[0141]
　 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.
[0142]
　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 film 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.
[0143]
　Tables 4-1 and 4-2 show the evaluation results of the film thickness of the SiO 2 intermediate oxide film layer, the degree of concentration of the interface-concentrating element by the GDS spectrum, and the film adhesion. The measurement and evaluation were carried out according to the measurement and evaluation of Example 1. When the formula (1) was satisfied, it was evaluated as "OK", and when it was not satisfied, it was evaluated as "NG".
[0144]
[Table 4-1]

[0145]
[Table 4-2]

[0146]
　D1 to D33 are examples of the invention. For the invented steels D1 to D4, the annealing time when forming the SiO 2 intermediate oxide film layer and the average heating rate HR2 in the temperature range of 600 ° C. to T1 ° C. are out of the preferable range, so that the film adhesion evaluation is performed. Although it was limited to "F", in the invention steels D5 to D11, although the selective element was not contained, the annealing time at the time of forming the SiO 2 intermediate oxide film layer and HR2 were controlled in a more preferable range. The evaluation of film adhesion was "G", which was a good result.
　With respect to the invention steels D12 to D22, in the invention steels D16 to D18, the annealing temperature, annealing time, and oxygen partial pressure at the time of forming the SiO 2 intermediate oxide film layer are all controlled within a preferable range, and the rate of temperature rise is high. Was controlled to a more preferable range, so that the film adhesion was particularly good and was "VG". In D12 to D15, the heating rate was controlled in a preferable range, but the annealing temperature was out of the preferable range, so the evaluation was “G”. Regarding D19 to D22, although the annealing temperature and annealing time were controlled to a preferable range and the heating rate was controlled to a more preferable range, the oxygen partial pressure was out of the preferable range, so the evaluation was "G". "was.
　The invented steels D23 to D33 contain the selective elements Cr, Ca, Cu, Sn and B. Therefore, it exhibits better film adhesion than other invention steels D1 to D22. For example, in D23 to D26, although the annealing temperature was out of the preferable range, the evaluation was "VG", which was a particularly good evaluation result. Further, although the invention steels D30 to D33 had an oxygen partial pressure outside the preferable range, the evaluation was "VG", which was a particularly good evaluation result.
[0147]
　On the other hand, d1 to d9 are comparative examples. In d1 ~ d3, d5, SiO 2 annealing temperature for forming an intermediate oxide layer, annealing time, and, for any of the oxygen partial pressure is outside the scope of the present invention, SiO 2 intermediate oxide layer Was not formed, and film adhesion could not be ensured. Further, in d1 to d3, since the peak derived from SiO 2 could not be observed by GDS , T p and T f could not be defined. Therefore, the column of "Surface GDS analysis formula (1) Al" in Table 4 is set to "-".
[0148]
　In d4, d8 and d9, although the SiO 2 intermediate oxide film layer could be formed, the cooling rate was high and the time for Al to concentrate at the interface between the SiO 2 intermediate oxide film layer and the steel sheet could not be secured, so that the film was formed. The evaluation of adhesion was B (no effect).
　Since HR2 was above the upper limit in d6 and HR2 was less than the lower limit in d7, many oxides other than SiO 2 were formed. Therefore, the evaluation of film adhesion was B.
Industrial applicability
[0149]
　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 insulating film having excellent film adhesion can be formed on the surface of the finish-annealed grain-oriented electrical 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 is
provided with an insulating film; as
a chemical component, in
　　terms of mass%, C: 0.010% or less;
　　Si: 2.50 to 4.00%;
　　Acid-soluble Al: 0.0010 to 0. It contains 0100%;
　　N: 0.012% or less;
　　Mn: 1.00% or less;
　　S: 0.02% or less;
the
　balance is
　composed of Fe and impurities, and the metal element M (M) of the intermediate oxide film layer. : A directional electromagnetic steel plate characterized in that the time differential curve f M (t ) of the glow discharge emission analysis spectrum of Al) satisfies the following equation (1)
.
[Equation 1]

　　T p : Time t (seconds)
　　T f corresponding to the minimum value of the second-order time derivative curve of the glow discharge emission analysis spectrum of Si. : Time t (seconds) corresponding to 2T p− T s , where T s is the analysis start point of the glow discharge emission analysis spectrum of Si.
[Claim 2]
　The base metal steel plate is a kind of
　　Cr: 0.01 to 0.50%;
　　Cu: 0.01 to 0.50%;
　　Ca: 0.001 to 0.05%;
in mass% as the chemical component. Alternatively, the time differential curve f M (t) of the glow discharge emission analysis spectrum of the metal element M (M: Cr, Cu, Ca) of the
　SiO 2 intermediate oxide film layer further containing two or more kinds is given by the following formula (2). The directional electromagnetic steel plate according to claim 1, wherein one or more of (4) to (4) are satisfied . [Number 2]

[Claim 3]
　The base steel sheet is characterized by further containing one or two kinds of
　　Sn: 0.01 to 0.20%;
　　B: 0.001 to 0.010%; in mass% as the chemical component. The directional electromagnetic steel sheet according to claim 1 or 2.

[Claim 4]
　The method for producing a directional electromagnetic steel plate according to any one of claims 1 to 3, 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 ,
　　Annealing temperature T1: 600-1200 ° C. Annealing time: 5-1200 seconds, oxygen partial pressure PH2O / PH2 : 0.15 or less, average heating rate in the temperature range of 600 ° C.-T1 ° C. HR2: 5-50 ° C. Annealing is performed under the condition of / sec;
　　after the 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 CR1. A
method for manufacturing a directional electromagnetic steel plate, characterized in that the temperature is less than .
　　Here, T2 ° C represents a temperature represented by T1 ° C-100 ° C.