Title of the invention: A coating liquid for forming an insulating film for grain-oriented electrical steel sheets, a method for manufacturing grain-oriented electrical steel sheets, and a method for manufacturing grain-oriented electrical steel sheets.
Technical field
[0001]
The present invention relates to a coating liquid for forming an insulating film for grain-oriented electrical steel sheets, a method for manufacturing grain-oriented electrical steel sheets, and a method for manufacturing grain-oriented electrical steel sheets.
Background technology
[0002]
The grain-oriented electrical steel sheet has a crystal structure whose main direction is (110) [001] orientation, and is usually a steel sheet containing 2% by mass or more of Si. Its main use is for iron core materials such as transformers, and in particular, materials with low energy loss during transformation, that is, materials with low iron loss are required.
[0003]
The typical manufacturing process of grain-oriented electrical steel sheets is as follows. First, a slab containing 2% by mass to 4% by mass of Si is hot-rolled to anneal the hot-rolled sheet. Next, cold rolling is performed once or twice or more with an intermediate annealing in between to obtain the final plate thickness, and decarburization annealing is performed. After that, an annealing separator mainly composed of MgO is applied and final finish annealing is performed. As a result, a crystal structure having the (110) [001] orientation as the main orientation is developed, and a finish annealing film mainly composed of Mg 2SiO 4 is formed on the surface of the steel sheet. Finally, the coating liquid for forming the insulating film is applied and baked, and then shipped.
[0004]
The grain-oriented electrical steel sheet has the property of improving iron loss by applying tension to the steel sheet. Therefore, by forming an insulating film made of a material having a coefficient of thermal expansion smaller than that of a steel sheet at a high temperature, tension is applied to the steel sheet, and iron loss can be improved.
[0005]
Conventionally, various coating liquids for forming an insulating film on an electromagnetic steel sheet have been known (see, for example, Patent Documents 1 to 11).
Prior art literature
Patent documents
[0006]
Patent Document 1: Japanese Patent Application Laid-Open No. 48-039338
Patent Document 2: Japanese Patent Publication No. 54-143737
Patent Document 3: Japanese Unexamined Patent Publication No. 2000-169972
Patent Document 4: Japanese Unexamined Patent Publication No. 2000-178760
Patent Document 5: International Publication No. 2015/115036
Patent Document 6: Japanese Patent Application Laid-Open No. 06-066754
Patent Document 7: Japanese Unexamined Patent Publication No. 06-066755
Patent Document 8: Japanese Unexamined Patent Publication No. 08-325745
Patent Document 9: Japanese Patent Application Laid-Open No. 09-256164
Patent Document 10: Japanese Unexamined Patent Publication No. 06-306628
Patent Document 11: Japanese Unexamined Patent Publication No. 2017-075358
Patent Document 12: International Publication No. 2010/146821
Outline of the invention
Problems to be solved by the invention
[0007]
The insulating film obtained by baking a coating liquid composed of colloidal silica, primary phosphate, and chromic acid disclosed in Patent Document 1 is excellent in various film characteristics such as tension.
[0008]
However, the coating liquid for forming the insulating film contains hexavalent chromium, and has consideration for equipment in order to improve the working environment in the insulating film forming process of the grain-oriented electrical steel sheet. Therefore, there is a long-awaited development of a coating liquid for forming an insulating film of grain-oriented electrical steel sheets, which does not contain hexavalent chromium and can obtain an insulating film having excellent various film characteristics such as tension.
[0009]
For example, Patent Documents 2 to 5 describe a coating liquid for forming an insulating film of a directional electromagnetic steel sheet, which mainly contains colloidal silica and primary phosphate and uses other additives instead of chromic acid. Has been done. However, the film tension of the insulating film obtained by the coating liquid for forming an insulating film that does not contain chromic acid and uses an additive other than chromic acid is the film of the insulating film obtained by the coating liquid for forming an insulating film containing chromic acid. Less than tension. In addition, all of the additives used in these techniques are more expensive than chromic acid.
[0010]
On the other hand, Patent Document 6 and Patent Document 7 disclose a coating liquid for forming an insulating film containing alumina sol and boric acid. Further, the coating liquids for forming an insulating film disclosed in Patent Documents 8 and 9 include alumina or alumina hydrate, an insulating film forming coating liquid containing boric acid, alumina or alumina hydrate, and boric acid. , A coating liquid for forming an insulating film containing colloidal silica and the like are disclosed. The film tension of the insulating film formed by baking these coating solutions is larger than that of the insulating film obtained by baking the coating solution composed of colloidal silica, primary phosphate, and chromic acid described above. Is obtained. Further, Patent Document 10 is coated with an aqueous solution sol containing aluminum oxide and boric acid by a method as disclosed in Patent Documents 6 and 7, whereby a crystalline film of xAl 203 · yB 2O 3 is formed. A directional electromagnetic steel plate with the above is disclosed.
However, since these insulating films are composed only of crystalline films of xAl 203 / yB 2O 3, there is room for further improvement from the viewpoint of corrosion resistance. In addition, many of the alumina sol used as a raw material are expensive.
[0011]
Hydrous silicate (layered clay mineral) can be mentioned as a substance whose raw material can be obtained at a relatively low price and which may obtain a large film tension after baking.
For example, Patent Document 11 discloses a coating liquid composed of kaolin, which is a kind of hydrous silicate, and lithium silicate. The insulating film obtained by baking the coating liquid described in this document has a film tension equal to or higher than that obtained by baking the coating liquid composed of colloidal silica, primary phosphate, and chromic acid. .. Further, the obtained grain-oriented electrical steel sheet has excellent iron loss. However, all of the insulating films made of these coating liquids lack precision. As a result, it was found that the use of these coating liquids may result in insufficient corrosion resistance of the insulating film.
Patent Document 12 discloses a coating liquid comprising a filler such as kaolin which is a kind of hydrous silicate and a binder containing a metal phosphate salt. In the insulating film obtained by baking this coating liquid at 250 to 450 ° C., kaolin, which is a kind of hydrous silicate, is dispersed as a filler. The local denseness of the insulating film changes depending on the dispersion state of the filler. As a result, it was found that the use of these coating liquids may result in insufficient corrosion resistance of the insulating film.
[0012]
Therefore, an object of the present invention is a coating liquid for forming an insulating film of a grain-oriented electrical steel sheet, which can obtain a film property having a large film tension and excellent corrosion resistance without using a chromium compound, and a grain-oriented electrical steel sheet. , And to provide a method for manufacturing grain-oriented electrical steel sheets.
Means to solve problems
[0013]
The means for solving the above problems include the following aspects.
[0014]
<1>
A coating liquid for forming an insulating film for grain-oriented electrical steel sheets, which contains hydrous silicate particles having aluminum and boric acid.
<2>
The coating liquid for forming an insulating film for grain-oriented electrical steel sheets according to <1>, wherein the specific surface area of ​​the hydrous silicate particles is 20 m 2 / g or more.
<3>
A coating for forming an insulating film for grain-oriented electrical steel sheets according to any one of <1> or <2>, wherein the hydrous silicate particles contain at least one particle of kaolin and pyrophyllite. liquid.
<4>
The content ratio of the hydrous silicate particles to the boric acid is 0.2 to 1.5 as a B (boron) / Al (aluminum) molar ratio in the coating liquid, <1> to <3>. A coating liquid for forming an insulating film for a directional electromagnetic steel plate according to any one of the above.
<5>
With the base material of grain-oriented electrical steel sheet,
An insulating film provided on the base material of the grain-oriented electrical steel sheet, which contains crystals of pseudo-tetragonal aluminum borate composed of constituent elements including Al, B, and O.
A grain-oriented electrical steel sheet with.
<6>
After applying the coating liquid for forming the insulating film for grain-oriented electrical steel sheets according to any one of <1> to <4> to the grain-oriented electrical steel sheets after final finish annealing, the temperature of the baking process. A method for manufacturing a grain-oriented electrical steel sheet, which comprises a step of performing a baking process having a temperature of 600 ° C. to 1000 ° C.
The invention's effect
[0015]
According to the present invention, a coating liquid for forming an insulating film of a grain-oriented electrical steel sheet, a coating liquid for forming an insulating film of grain-oriented electrical steel sheet, and a grain-oriented electrical steel sheet, which have a large film tension and can obtain film characteristics having excellent corrosion resistance without using a chromium compound, and a grain-oriented electrical steel sheet. A method for manufacturing a grain-oriented electrical steel sheet is provided.
A brief description of the drawing
[0016]
[Fig. 1] Fig. 1 is a cross-sectional photograph showing an example of a grain-oriented electrical steel sheet provided with a conventional insulating film.
FIG. 2 is a cross-sectional photograph of a grain-oriented electrical steel sheet provided with an insulating film in Example 10.
FIG. 3 is a graph showing the results of X-ray crystal structure analysis of the insulating film in Example 10.
Embodiment for carrying out the invention
[0017]
Hereinafter, an example of a preferred embodiment of the present invention will be described.
In the present specification, the numerical range represented by using "-" means a range including the numerical values ​​before and after "-" as the lower limit value and the upper limit value.
In the present specification, the term "process" is used not only as an independent process but also as long as the intended purpose of the process is achieved even if it cannot be clearly distinguished from other processes. included.
[0018]

The coating liquid for forming the insulating film for grain-oriented electrical steel sheets (coating liquid for forming the insulating film) according to the present embodiment contains hydrous silicate particles having aluminum and boric acid.
[0019]
As described above, as a coating liquid for forming an insulating film that does not use a chromium compound, for example, a coating liquid for forming an insulating film containing alumina sol and boron has been studied. An insulating film is formed by applying this insulating film-forming coating liquid onto a base material of a grain-oriented electrical steel sheet and then baking it. The insulating film of the grain-oriented electrical steel sheet obtained by the coating liquid for forming an insulating film containing alumina sol and boron contains aluminum borate crystals and has excellent film tension. However, although the cause is not clear, this insulating film may have inferior corrosion resistance. Therefore, there is room for improving the corrosion resistance while ensuring the characteristic that excellent film tension can be obtained in the insulating film.
[0020]
Therefore, after ensuring excellent film tension, we examined the improvement of corrosion resistance of the insulating film. As a result, it was found that by combining the hydrous silicate particles and boric acid, an insulating film of grain-oriented electrical steel sheet having excellent film tension and improved corrosion resistance can be obtained. This insulating film becomes a dense insulating film. Therefore, it has a film tension equal to or higher than that of the conventional insulating film. Further, it is considered that better corrosion resistance can be obtained than the insulating film obtained by the coating liquid for forming an insulating film containing alumina sol and boron.
[0021]
Hereinafter, each material constituting the coating liquid according to the present embodiment will be described.
[0022]
(Hydrohydrated silicate particles)
The coating liquid for forming an insulating film contains hydrous silicate particles. The hydrous silicate particles may be contained in one kind or two or more kinds.
Hydrous silicates are also called clay minerals and often have a layered structure. The layered structure consists of a 1: 1 silicate layer represented by the composition formula X 2-3Si 2O 5 (OH) 4 and the composition formula X 2-3 (Si, Al) 4O 10 (OH) 2 (X is Al, Mg). , Fe, etc.) and the 2: 1 silicate layer are laminated alone or mixed. The layers of the layered structure may contain at least one of a water molecule and an ion.
[0023]
Typical hydrous silicates are kaolin (or kaolinite) (Al 2Si 2O 5 (OH) 4), talc (Mg 3Si 4O 10 (OH) 2), pyrophyllite (Al 2Si 4O 10 (OH) 4). ) 2) can be mentioned. Most of the hydrous silicate particles are purified and pulverized naturally occurring hydrous silicate. As the hydrous silicate particles, it is preferable to use at least one kind of particles selected from the group consisting of kaolin, talc, and pyrophyllite from the viewpoint of industrial availability. Further, from the viewpoint of obtaining excellent film tension and excellent corrosion resistance, hydrous silicate particles containing aluminum are used. Hydrous silicate particles containing aluminum have excellent reactivity with boric acid, and pseudotetragonal aluminium borate. It produces a film, and excellent film tension and excellent corrosion resistance can be obtained. From this point of view, it is preferable to use at least one kind of particles of kaolin and pyrophyllite as the hydrous silicate particles, and it is more preferable to use kaolin. The hydrous silicate particles may be used in combination.
[0024]
The larger the specific surface area of ​​the hydrous silicate particles, the easier it is for the reaction with boric acid to be promoted. Therefore, the specific surface area of ​​the hydrous silicate particles is preferably 20 m 2 / g or more, more preferably 40 m 2 / g or more, and further preferably 50 m 2 / g or more.
On the other hand, the upper limit of the specific surface area is not particularly limited, and the specific surface area may be 200 m 2 / g or less, 180 m 2 / g or less, or 150 m 2 / g or less. When the upper limit of the specific surface area is not more than the above, it becomes easy to maintain the dispersion stability (viscosity stability) of the coating liquid for forming the insulating film. The specific surface area of ​​the hydrous silicate particles is the specific surface area based on the BET method, and is measured by a method based on JIS Z 8830: 2013.
[0025]
(Production of hydrous silicate particles with a specific surface area of ​​20 m 2 / g or more)
It is difficult to obtain hydrous silicate particles having a specific surface area of ​​20 m 2 / g or more, which are commercially available for industrial use. Therefore, for example, by subjecting a commercially available product to a pulverization treatment, hydrous silicate particles having a specific surface area of ​​20 m 2 / g or more can be obtained.
[0026]
As a means for crushing hydrous silicate particles, a ball mill, a vibration mill, a bead mill, a jet mill, or the like is effective. In these pulverization treatments, dry pulverization may be performed in which the powder is pulverized as it is, or wet pulverization may be performed in a slurry state in which hydrous silicate particles are dispersed in a dispersion medium such as water or alcohol. The pulverization treatment is effective in both dry pulverization and wet pulverization. The specific surface area of ​​the hydrous silicate particles also increases with the grinding time by various grinding means. Therefore, by controlling the crushing time for the specific surface area of ​​the hydrous silicate particles, the hydrous silicate particles having a required specific surface area and the dispersion liquid thereof can be obtained.
[0027]
The hydrous silicate may be plate-like particles, because in many cases, the hydrous silicate has a layered structure, that is, a structure in which a plurality of layers are laminated. Delamination occurs due to the crushing process. That is, the pulverization treatment reduces the thickness of the plate-shaped particles of the plate-shaped hydrous silicate. The thinner this thickness, the easier it is for the reaction with boric acid to be promoted. Therefore, the thickness of the hydrous silicate particles (plate-like particles) is preferably 0.1 μm or less, more preferably 0.05 μm or less, and further preferably 0.02 μm or less.
On the other hand, the lower limit of the thickness of the hydrous silicate particles (plate-like particles) is not particularly limited, but may be 0.001 μm or more because the viscosity becomes high when the particle surface is activated and suspended in water. , It may be preferably 0.002 μm or more, and more preferably 0.005 μm or more.
The thickness of the hydrous silicate particles (plate-like particles) is determined by analyzing an image of the hydrous silicate particle shape obtained by a scanning electron microscope or a transmission electron microscope.
[0028]
In the case of wet pulverization treatment, the viscosity of the dispersion liquid increases as the specific surface area of ​​the hydrous silicate particles increases. When the specific surface area is increased to exceed 200 m 2 / g by pulverization, the viscosity of the dispersion liquid may increase and gel, which may interfere with the pulverization treatment. Therefore, if necessary, a dispersant may be added to the dispersion.
[0029]
The increase in viscosity during the crushing process can be suppressed by adding a dispersant. However, among the dispersants, if an organic dispersant is added, it may be decomposed and carbonized during baking of the insulating film and carburized in the grain-oriented electrical steel sheet. Therefore, when a dispersant is used, an inorganic dispersant is preferable. .. Examples of the inorganic dispersant include polyphosphate, water glass and the like. Specific dispersants of the former include sodium diphosphate and sodium hexametaphosphate. Specific dispersants for the latter include sodium silicate and potassium silicate.
The amount of these inorganic dispersants added is preferably suppressed to 20% by mass or less with respect to the total mass of the hydrous silicate particles. By setting the addition amount of the inorganic dispersant to 20% by mass or less, the change in the film composition after baking is suppressed, and a higher film tension can be easily obtained. Since the dispersant is an optional additional component, the lower limit of the dispersant is not particularly limited and may be 0%. That is, the coating liquid may not contain a dispersant such as polyphosphate and water glass.
In the case of dry crushing treatment, it is not necessary to add a dispersant at the time of crushing.
[0030]
(Boric acid)
As the boric acid, those obtained by a known production method can be used, and either orthoboric acid or metaboric acid may be used. As boric acid, orthoboric acid may be used. Boric acid may be used as particulate boric acid, or may be used after dissolving or dispersing boric acid in water.
[0031]
(Content ratio of hydrous silicate particles and boric acid)
The content ratio of the hydrous silicate particles contained in the coating liquid for forming an insulating film and boric acid is not particularly limited as the B (boron) / Al (aluminum) molar ratio. The B (boron) / Al (aluminum) molar ratio is preferably 1.5 or less from the viewpoint of obtaining excellent film tension and excellent corrosion resistance. Boric acid and borate have relatively low solubility in water. Therefore, if the B / Al molar ratio is made too large, the concentration of the coating liquid must be reduced, and it becomes difficult to obtain the desired amount of film. Therefore, the upper limit of the B / Al molar ratio is preferably 1.5 or less, preferably 1.3 or less, and more preferably 1.0 or less. The lower limit of the B / Al molar ratio is not particularly limited, and may be 0.05 or more, or 0.1 or more. From the viewpoint of obtaining excellent film tension and excellent corrosion resistance, the lower limit of the B / Al molar ratio is preferably 0.2 or more. Therefore, the content ratio of the hydrous silicate particles to boric acid is preferably 0.2 to 1.5 as a B (boron) / Al (aluminum) molar ratio.
[0032]
(Dispersion medium (or solvent))
As the dispersion medium or solvent used in the coating liquid for forming an insulating film, alcohols such as ethyl alcohol, methyl alcohol, and propyl alcohol can be used in addition to water. As the dispersion medium or solvent, it is preferable to use water from the viewpoint of not having flammability.
[0033]
The solid content concentration of the coating liquid for forming an insulating film is not particularly limited as long as it can be applied to grain-oriented electrical steel sheets. The solid content concentration of the coating liquid for forming an insulating film may be, for example, in the range of 5% by mass to 50% by mass (preferably 10% by mass to 30% by mass).
[0034]
Further, the coating liquid for forming an insulating film according to the present embodiment may or may not contain a small amount of other additives, if necessary, as long as the characteristics of film tension and corrosion resistance are not impaired. Good (0% by mass). When a small amount of other additives is contained, for example, it is preferably 3% by mass or less, and preferably 1% by mass or less, based on the total solid content of the coating liquid for forming an insulating film according to the present embodiment. Examples of other additives include, for example, a surfactant that prevents the coating liquid from repelling on the steel sheet.
[0035]
The viscosity of the coating liquid for forming an insulating film is preferably 1 mPa · s to 100 mPa · s from the viewpoint of coating workability and the like. If the viscosity is too high, it may be difficult to apply, and if the viscosity is too low, the coating liquid may flow and it may be difficult to obtain the desired amount of film. The measurement is performed by a B-type viscometer (Brookfield-type viscometer). The measured temperature is 25 ° C.
[0036]
From the viewpoint of the working environment, it is preferable that the coating liquid for forming an insulating film does not contain hexavalent chromium. Further, the insulating film obtained by the coating liquid for forming an insulating film according to the present embodiment is baked at a high temperature (for example, 600 ° C. or higher) in order to obtain a high tension. Therefore, when the resin is contained in the coating liquid for forming the insulating film, the resin is decomposed and carburized by baking. As a result, the magnetic properties of the grain-oriented electrical steel sheet are deteriorated. From this point of view, it is preferable that the coating liquid for forming an insulating film does not contain an organic component such as a resin.
[0037]
Here, the coating liquid for forming an insulating film according to the present embodiment can apply tension to the steel sheet by baking, and is suitable as a coating liquid for forming an insulating film of a grain-oriented electrical steel sheet. The coating liquid for forming an insulating film according to this embodiment can also be applied to non-oriented electrical steel sheets. However, even if the coating liquid for forming an insulating film according to the present embodiment is applied to a non-oriented electrical steel sheet, the insulating film does not contain an organic component and there is no effect of improving the punching property of the steel sheet. Therefore, the benefit of application to non-oriented electrical steel sheets is small.
[0038]
(Preparation method of coating liquid)
The coating liquid for forming an insulating film according to this embodiment may be prepared by mixing and stirring hydrous silicate particles and boric acid together with a dispersion medium (solvent). The order of addition of the hydrous silicate particles and boric acid is not particularly limited. For example, a dispersion liquid in which a predetermined amount of hydrous silicate particles are dispersed in water as a dispersion medium may be prepared, and then a predetermined amount of boric acid may be added to mix and stir. Alternatively, after preparing a boric acid aqueous solution in which a predetermined amount of boric acid is dissolved in water as a solvent, a predetermined amount of hydrous silicate particles may be added to the boric acid aqueous solution and mixed and stirred.
Also, if necessary, other additives may be added and mixed and stirred. Then, the coating liquid for forming an insulating film may be adjusted to a desired solid content concentration. The liquid temperature of the coating liquid may be heated (for example, 50 ° C.) or normal temperature (for example, 25 ° C.).
[0039]
(Analysis of components of coating liquid)
In the coating liquid for forming an insulating film according to the present embodiment, the hydrous silicate particles and boric acid in the coating liquid can be measured as follows.
The coating liquid mixed with hydrous silicate particles and boric acid hardly reacts at 100 ° C or lower. Therefore, the coating liquid at 100 ° C. or lower is in a slurry state in which hydrous silicate particles are dispersed in, for example, a boric acid aqueous solution.
Specifically, first, the coating liquid for forming an insulating film is filtered. By filtering, the coating liquid is separated into a filtrate containing a boric acid aqueous solution derived from boric acid before mixing and a residue containing a hydrous silicate derived from hydrous silicate particles. Next, ICP-AES analysis (high frequency inductively coupled plasma-atomic emission spectroscopic analysis) of the filtrate reveals that it contains boric acid. In addition, fluorescent X-ray analysis of the residue reveals the molar ratio of boron to aluminum in the hydrous silicate (B / Al).
Further, the specific surface area of ​​the hydrous silicate particles is such that the hydrous silicate particles separated above are dispersed in a solvent in which the hydrous silicate particles are not dissolved. After that, the specific surface area is determined by the above-mentioned BET method. Further, the thickness of the hydrous silicate particles (plate-like particles) can be determined by the above-mentioned observation with an electron microscope.
[0040]

Next, an example of a preferred embodiment of the grain-oriented electrical steel sheet and the method for manufacturing the grain-oriented electrical steel sheet according to the present embodiment will be described.
[0041]
The grain-oriented electrical steel sheet according to the present embodiment is an insulating film provided on the base material of the grain-oriented electrical steel sheet and the base material of the grain-oriented electrical steel sheet, and is composed of constituent elements including Al, B, and O. It has an insulating film containing crystals of pseudo-square crystal aluminum borate. The insulating film is composed of a reaction product of boric acid and a hydrous silicate having aluminum, and crystals of pseudorectangular aluminum borate composed of constituent elements including Al, B, and O are formed in at least a part of the insulating film. Contains.
[0042]
In the grain-oriented electrical steel sheet according to the present embodiment, the insulating film containing crystals of pseudotetragonal aluminum borate composed of constituent elements including Al, B, and O is different from the conventional insulating film.
For example, the insulating film formed of phosphate, colloidal silica, and chromic acid based on Patent Documents 1 to 4 is an amorphous substance containing Al, Mg, P, Si, Cr, and O as constituent elements. Further, the insulating film using alumina sol and boric acid represented by Patent Document 6 is shown in Patent Document 10. As shown above, it is composed only of a crystalline substance represented by the composition formula xAl 203 · yB 2O 3 having Al, B, and O as constituent elements.
On the other hand, the insulating film according to the present embodiment is composed of pseudorectangular aluminum borate xAl 203 · yB 2O 3 generated by the reaction of the Al component in the hydrous silicate particles with boric acid, and the hydrous silicate particles. It is composed of an amorphous component caused by a residual component other than Al. For example, when kaolin is used as the hydrous silicate particles, it becomes a mixture of pseudotetragonal aluminum borate and silica as follows. Therefore, the composition of the insulating film in the grain-oriented electrical steel sheet according to the present embodiment is different from that of the conventional insulating film.
2yH 3BO 3 + xAl 2Si 2O 5 (OH) 4
→ xAl 2O 3 ・ yB 2O 3 + 2xSiO 2 + (2x + 3y) H 2O
[0043]
The directional electromagnetic steel plate according to the present embodiment has an excellent film tension because the insulating film contains crystals of pseudotetragonal aluminum borate composed of constituent elements including Al, B, and O. In addition, it has excellent corrosion resistance due to the structure in which the crystalline phase is surrounded by an amorphous layer. Further, a dense film is formed as the insulating film of the grain-oriented electrical steel sheet according to the present embodiment. The grain-oriented electrical steel sheet according to this embodiment is preferably obtained by the manufacturing method described below.
[0044]
The method for manufacturing a grain-oriented electrical steel sheet according to the present embodiment is to apply an insulating film for grain-oriented electrical steel sheet according to the present embodiment to the grain-oriented electrical steel sheet (that is, the base material of the grain-oriented electrical steel sheet) after final finish annealing. After applying the coating liquid for forming, there is a step of performing a baking treatment in which the temperature of the baking treatment is 600 ° C. to 1000 ° C.
[0045]
(Directive electrical steel sheet after final finish annealing)
The grain-oriented electrical steel sheet after final finish annealing is a grain-oriented electrical steel sheet which is a base material before applying the above-mentioned coating liquid (that is, the coating liquid for forming an insulating film according to the present embodiment). The grain-oriented electrical steel sheet after final finish annealing is not particularly limited. The grain-oriented electrical steel sheet used as a base material is obtained as follows as a suitable example. Specifically, for example, a steel piece containing 2% by mass to 4% by mass of Si is hot-rolled, hot-rolled, and cold-rolled, and then decarburized and annealed. After that, it is obtained by applying an annealing separator having an MgO content of 50% by mass or more and performing final finish annealing. The grain-oriented electrical steel sheet after final finish annealing does not have to have a finish annealing film.
[0046]
(Applying and baking treatment of coating liquid for forming insulating film)
After applying the insulating film forming coating liquid according to this embodiment to the grain-oriented electrical steel sheet after final finish annealing, baking treatment is performed. The coating amount is not particularly limited. From the viewpoint of obtaining excellent film tension and excellent corrosion resistance, it is preferable to apply the film so that the amount of the film after forming the insulating film is in the range of 1 g / m 2 to 10 g / m 2. More preferably, it is 2 g / m 2 to 8 g / m 2. The coating amount after the baking treatment can be obtained from the weight difference before and after the insulating film is peeled off.
Further, the excellent film tension and corrosion resistance may be equal to or higher than that of a conventional insulating film, particularly an insulating film when a coating liquid containing a chromium compound is used. In the reference example (insulating film when a coating liquid containing a chromium compound is used) described later, the film tension is 8 MPa and the corrosion resistance is 0%. In the insulating film according to the present embodiment, the film tension may be 5 MPa or more, preferably 8 MPa or more, and more preferably 10 MPa or more in consideration of the allowable likelihood. Further, the corrosion resistance may be 10% or less, preferably 5% or less, more preferably 1% or less, or 0%.
[0047]
The method of applying the coating liquid for forming an insulating film to the grain-oriented electrical steel sheet after final finish annealing is not particularly limited. For example, a coating method using a coating method such as a roll method, a spray method, or a dip method can be mentioned.
[0048]
After applying the coating liquid for forming an insulating film, baking is performed. It forms a dense film and promotes the reaction between hydrous silicate particles and boric acid from the viewpoint of obtaining excellent film tension and excellent corrosion resistance. Many hydrous silicates release structural water near a heating temperature of 550 ° C and react with boric acid in the process. If the baking temperature is less than 600 ° C., the reaction between the hydrous silicate particles and boric acid is not sufficient. Therefore, each of the hydrous silicate particles and boric acid forms a mixed insulating film. Therefore, the baking temperature is set to 600 ° C. or higher. The preferable lower limit of the baking temperature is 700 ° C. or higher. On the other hand, when a baking temperature of more than 1000 ° C. is adopted, the grain-oriented electrical steel sheet is softened and easily distorted, so the baking temperature is set to 1000 ° C. or less. The preferred upper limit is 950 ° C. or lower. The baking time is preferably 5 seconds to 300 seconds (preferably 10 seconds to 120 seconds).
[0049]
The heating method for performing the baking process is not particularly limited, and examples thereof include a radiant furnace, a hot air furnace, and induction heating.
[0050]
The insulating film after baking is a dense film. The thickness of the insulating film is preferably 0.5 μm to 5 μm (preferably 1 μm to 4 μm).
The thickness of the insulating film after the baking treatment can be obtained by observing the cross section SEM.
[0051]
Denseness can be evaluated by the void ratio in the film. When a large amount of voids are present in the film, the insulating film is considered to have low film tension and inferior corrosion resistance. In the insulating film according to the present embodiment, the void ratio may be 10% or less, preferably 5% or less, more preferably 3% or less, more preferably 2% or less, and particularly preferably 1% or less.
[0052]
By the above steps, the coating liquid for forming an insulating film according to the present embodiment can obtain a grain-oriented electrical steel sheet having excellent both film tension and corrosion resistance even if it does not contain a chromium compound. Further, the grain-oriented electrical steel sheet provided with the insulating film by the coating liquid for forming the insulating film according to the present embodiment is excellent in magnetic properties and also excellent in space factor.
[0053]
When evaluating film characteristics, corrosion resistance, magnetic properties, void ratio of insulating film, etc. with respect to the grain-oriented electrical steel sheet with insulating film obtained by this embodiment, the evaluation method for each evaluation is as follows.
[0054]
(Corrosion resistance)
While keeping the temperature at 35 ° C., a 5 mass% NaCl aqueous solution was continuously sprayed onto the test piece, the state of rust generation after 48 hours had elapsed, and the area ratio was calculated.
[0055]
(Film tension)
The film tension is calculated from the warp of the steel sheet that occurs when one side of the insulating film is peeled off. The specific conditions are as follows.
Remove the one-sided insulating film provided on the grain-oriented electrical steel sheet with an alkaline aqueous solution. After that, the film tension is obtained from the warp of the grain-oriented electrical steel sheet by the following formula.
Formula: Film tension = 190 x plate thickness (mm) x plate warp (mm) / {plate length (mm)} 2 [MPa]
[0056]
(Fortune-telling rate)
Measure according to the method described in JIS C 2550-5: 2011.
[0057]
(Film void ratio)
Obtain an image of the cross section of the insulating film by backscattered electrons. This image is binarized to obtain a binary image. The area AC of the cross section obtained by excluding the area of ​​the voids (pores) from this binary image is obtained.
Obtain the cross-sectional area A including the area of ​​the void (pore) from the binary image filled with the void. Then, the void ratio F is obtained by the following formula (F).
Observe the insulating film at a magnification of 5000 times to obtain 5 images, and calculate the average value from the obtained void ratio.
Formula (F) F = {1- (AC / A)} x 100
[0058]
(Iron loss and magnetic flux density)
The iron loss and the magnetic flux density are measured according to the method described in JIS C 2550-1: 2011. Specifically, it is measured as iron loss (W 17/50) per unit mass under the condition that the amplitude of the measured magnetic flux density is 1.7 T and the frequency is 50 Hz. Further, the magnetic flux density (B 8) measures the value of the magnetic flux density at a magnetization force of 800 A / m.
[0059]
Although an example of a preferred embodiment of the present invention has been described, the present invention is not limited to the above. The above is an example, and any material having substantially the same configuration as the technical idea described in the claims of the present invention and having the same effect and effect is the technique of the present invention. It is included in the scope.
Example
[0060]
Hereinafter, the present invention will be specifically described by exemplifying examples, but the present invention is not limited thereto.
[0061]
(Example A)
First, commercially available hydrous silicate particles of kaolin, talc, and pyrophyllite (specific surface area of ​​10 m 2 / g) were prepared and pulverized by various means shown in Table 1 below. When the dispersant was added, it was added at the time of preparing the water slurry before the treatment in the wet pulverization, and at the time of adjusting the coating liquid after the pulverization in the dry pulverization. After the pulverization treatment, the specific surface area was measured according to the method described in JIS Z 8830: 2013.
[0062]
Using the above hydrous silicate particles, a coating liquid having the composition shown in Table 1 was prepared. In order to confirm the stability of the coating liquid, a part of the preparation liquid was sampled and left at room temperature (25 ° C.) for 2 days and nights, and then the state of the coating liquid (presence or absence of gelation) was observed. The coating liquid shown in Example 22 is an example in which two types of hydrous silicate particles are mixed and used. As a result of observation, no gelation was observed in any of the coating liquids having the compositions shown in Table 1.
[0063]
A grain-oriented electrical steel sheet (B8 = 1.93T) having a thickness of 0.23 mm and having a finish annealing film for which final finish annealing has been completed is prepared, and the coating liquid having the composition shown in Table 1 is applied to the insulating film amount after baking. The coating was applied and dried so as to have a temperature of 5 g / m 2, and an annealing treatment was performed at 850 ° C. for 30 seconds.
[0064]
The film characteristics and corrosion resistance of the obtained grain-oriented electrical steel sheet with an insulating film were evaluated. In addition, the magnetic characteristics were evaluated. Furthermore, the void ratio of the insulating film was measured. The results are shown in Table 2. The evaluation method of each evaluation shown in Table 2 is as described above.
[0065]
The molar ratio of B / Al shown in Table 1 is a calculated value obtained by mixing and adjusting hydrous silicate particles and boric acid so that the molar ratio of B / Al becomes the value shown in Table 1.
[0066]
[table 1]

[0067]
[Table 2]

[0068]
The composition of the reference coating liquid in Table 1 is as follows.
・ Colloidal silica 20% by mass aqueous dispersion: 100 parts by mass
-Aluminum phosphate 50% by mass aqueous solution: 60 parts by mass
・ Chromic anhydride: 6 parts by mass
[0069]
The composition of the comparative coating liquid 1 in Table 1 is as follows.
Alumina sol with a solid content of 10% by mass: 100 parts by mass
-Boric acid: 7 parts by mass
[0070]
The solid content concentrations (mass%) of the hydrous silicate particles (clay mineral particles) and boric acid in Table 1 are calculated as anhydrous equivalents, for example, kaolin is Al 2O 3.2SiO 2 and boric acid is B 2O 3. Is.
[0071]
The crushing means in Table 1 are as follows.
JM: Jet mill (dry type)
BD: Ball mill (dry type)
BW: Ball mill (wet)
BM: Bead mill (wet)
[0072]
As shown in Table 1, Examples 1 to 36 are insulating films formed by using a coating liquid for forming an insulating film containing hydrous silicate particles and boric acid. As shown in Table 2, the insulating film of each example has a large film tension and is excellent in corrosion resistance. Furthermore, it is also excellent in space factor and magnetic properties.
Further, it can be seen that the insulating film of each example can obtain the same or higher performance as the film when the coating liquid containing the chromium compound shown in the reference example is used.
[0073]
On the other hand, it can be seen that the insulating film formed by using the coating liquid for forming an insulating film containing hydrous silicate particles and not containing boric acid is inferior in corrosion resistance. Further, it can be seen that the insulating film of Comparative Example 1 obtained by the coating liquid containing alumina sol and boric acid is inferior in corrosion resistance.
[0074]
Here, FIG. 1 shows an example of the result of observing the cross section of the conventional grain-oriented electrical steel sheet provided with the conventional insulating film by SEM. Also, in Fig. 2. , The result of observing the cross section of the grain-oriented electrical steel sheet provided with the insulating film of Example 10 by SEM is shown. In FIG. 1, 11 represents an insulating film and 12 represents a finish annealed film. Further, in FIG. 2, 21 represents an insulating film and 22 represents a finish annealed film. Hereinafter, the reference numerals will be omitted.
[0075]
The insulating film shown in FIG. 1 has a large amount of voids. Therefore, it is considered that the insulating film shown in FIG. 1 has a low film tension and is inferior in corrosion resistance. On the other hand, it was clarified that the insulating film shown in FIG. 2 is a dense film having extremely few voids. Therefore, it is considered that the insulating film shown in FIG. 2 has a high film tension and is also superior in corrosion resistance.
Therefore, the directional electromagnetic steel plate obtained by using the coating liquid for forming an insulating film of the present embodiment has a densified insulating film, has a large film tension even without using a chromium compound, and has corrosion resistance. It can be seen that excellent film characteristics can be obtained. Further, it can be seen that these film characteristics are obtained, and that the magnetic characteristics and the space factor are also excellent.
[0076]
FIG. 3 shows the results of X-ray crystal structure analysis of the insulating film of Example 10 using an X-ray diffractometer. From the graph shown in FIG. 3, it can be seen that the insulating film of Example 10 is composed of constituent elements including Al, B, and O, and contains pseudotetragonal aluminum borate.
[0077]
(Example B)
Next, the baking temperature is changed and the film characteristics and magnetic characteristics are evaluated. The coating liquid adjusted to the same composition as in Example 10 is coated and dried by the same procedure as in Example 1 so that the amount of the insulating film after the baking treatment is 5 g / m 2. Then, the baking temperature is changed to the conditions shown in Table 3 and the baking process is performed (the baking time is the same). The results are shown in Table 3.
[0078]
[Table 3]

[0079]
As shown in Table 3, Comparative Examples 6 and 7 having a baking temperature of less than 600 ° C. are inferior in corrosion resistance because the reaction between the hydrous silicate particles and boric acid is not sufficient. On the other hand, in each example in which the baking temperature is 600 ° C. or higher, excellent corrosion resistance can be obtained.
[0080] [0080]
Although the preferred embodiments of the present invention have been described above, the present invention is not limited to such examples. It is clear that a person skilled in the art can come up with various modifications or modifications within the scope of the ideas described in the claims, and these also naturally belong to the technical scope of the present invention. It is understood that it is a thing.
The scope of the claims
[Claim 1]
A coating liquid for forming an insulating film for grain-oriented electrical steel sheets, which contains hydrous silicate particles having aluminum and boric acid.
[Claim 2]
The coating liquid for forming an insulating film for grain-oriented electrical steel sheets according to claim 1, wherein the specific surface area of ​​the hydrous silicate particles is 20 m 2 / g or more.
[Claim 3]
The coating liquid for forming the insulating film for a directional electromagnetic steel plate according to claim 1 or 2, wherein the hydrous silicate particles contain at least one particle of kaolin and pyrophyllite.
[Claim 4]
Claims 1 to 3 in which the content ratio of the hydrous silicate particles to the boric acid is 0.2 to 1.5 as a B (boron) / Al (aluminum) molar ratio in the coating liquid. A coating liquid for forming an insulating film for a directional electromagnetic steel plate according to any one of the above items.
[Claim 5]
With the base material of grain-oriented electrical steel sheet,
An insulating film provided on the base material of the grain-oriented electrical steel sheet, which contains crystals of pseudo-tetragonal aluminum borate composed of constituent elements including Al, B, and O.
A grain-oriented electrical steel sheet with.
[Claim 6]
After applying the coating liquid for forming the insulating film for grain-oriented electrical steel sheets according to any one of claims 1 to 4 to the grain-oriented electrical steel sheets after final finish baking, the temperature of the baking process. A method for manufacturing a grain-oriented electrical steel sheet, which comprises a step of performing a baking process having a temperature of 600 ° C. to 1000 ° C.