JP2009007642A - Method for producing {100} texture silicon steel sheet - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method capable of stably producing a ä100} textile silicon steel sheet excellent in magnetic characteristic even in the case of a large scale laminate annealing or coil annealing while capable of largely reducing cost. <P>SOLUTION: The method for producing a ä100} textile silicon steel sheet comprises: a slurry coating step wherein a slurry containing annealing separation agent particles comprising at least either of a substance accelerating decarbonization and a substance accelerating decarbonization and demanganese, with a mass after drying of at least 80 g/m<SP>2</SP>, is applied to the surface of a cold rolled steel sheet containing 0.02-0.15 mass% C and containing Si and Mn in a range satisfying Si+Mn/2≤5.0 and Si-Mn/2≥1.5, and dried; and a final annealing step wherein laminate annealing or coil annealing is applied on the cold rolled steel sheet coated with the slurry and dried. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a method for manufacturing a silicon steel sheet having a {100} texture.

  Conventionally, silicon steel plates have been used for magnetic core materials such as electric motors, generators, and transformers. The magnetism required for this silicon steel sheet is that the magnetic energy loss is small in an alternating magnetic field and the magnetic flux density is high in a practical magnetic field. In order to realize these, it is effective to increase the electrical resistance and to integrate the <100> axis of the bcc lattice, which is the direction of easy magnetization, in the direction of the used magnetic field. In particular, in order to dramatically improve the magnetic characteristics, it is the most effective method to integrate the <100> axis, which is the easy magnetization direction, in the direction of the magnetic field used.

  For this reason, it is desired to develop a texture as shown in FIG. The texture shown in FIG. 1 (a) is a structure in which the {110} plane is parallel to the plate surface, and the <100> axis is accumulated in the rolling direction, like the core of a transformer using a wound core. Suitable for applications in which magnetic flux flows only in the direction. A silicon steel sheet having this texture is called a unidirectional silicon steel sheet. On the other hand, in the texture shown in FIGS. 1 (b) to (d), the {100} plane is parallel to the plate surface, so that the two <100> axes of the crystal are parallel to the plate surface, It is suitable not only for rotating machines. A silicon steel sheet having this texture is called a {100} texture silicon steel sheet. The orientation of the <100> axis in the plate surface of the {100} textured silicon steel plate is arbitrary, but in particular, the <100> axis is in the rolling direction and the plate width direction in the plate surface shown in Fig. 1 (b). The accumulated {100} <001> texture is called a bi-directional silicon steel sheet because it exhibits extremely excellent magnetic properties in these two directions. A silicon steel sheet having this texture is optimal for applications in which magnetic flux flows in the rolling direction and in the sheet width direction, such as a transformer core using a stacked iron core, in addition to a transformer using a wound iron core.

As a method for producing such a {100} texture silicon steel sheet, a production method using high-temperature annealing that causes decarburization or decarburization and de-Mn has been disclosed in recent years.
Patent Document 1 discloses decarburization as an annealing separator on a cold rolled silicon steel sheet containing C: 1% or less by weight, Si: 0.2 to 6.5%, and Mn: 0.05 to 5%. A method for producing a silicon steel sheet having a texture in which {100} is parallel to the plate surface, which is subjected to tight coil annealing or lamination annealing using a substance that promotes or a substance that promotes decarburization and a substance that promotes de-Mn. It is disclosed.
Further, in Patent Document 2 and Patent Document 3, {100} is parallel to the plate surface by performing the cold rolling step in the above-described silicon steel sheet manufacturing method as a plurality of cold rolling processes with intermediate annealing interposed therebetween. And a method for producing a silicon steel sheet having a structure in which the <001> axis is parallel to the rolling direction, that is, a method for producing a bidirectional silicon steel sheet is disclosed.
Patent Document 4 discloses that a sheet formed by adding a binder to an oxide fiber or powder containing SiO ₂ , Al ₂ O ₃ , TiO ₂ or the like is disclosed as an annealing separator.

By using the above-described method, a {100} texture silicon steel plate with good magnetic properties can be produced. Although these methods are very excellent technologies, there is room for further improvement from the viewpoint of cost.
For example, Patent Document 1 and Patent Document 2 recommend a method in which a fiber-like or fiber-like sheet-like annealing separator is produced separately from a steel plate, and the annealing separator is sandwiched between steel plates and annealed. Also in the example of Patent Document 3, a fibrous annealing separator is used. Patent Document 4 proposes that a long sheet is produced by adding a binder to ceramic fibers or powder. Obviously, producing a sheet-like annealing separator by a separate process leads to a significant increase in cost. In addition, the thickness of the sheet-like annealed separator is usually as thin as 0.5 mm or less, and a large amount of binder is required to ensure the strength required for handling. The bonding material is decomposed and dispersed in the final annealing, but if a large amount of the bonding material is used, there may be a problem that the inside of the annealing furnace is contaminated by a large amount of decomposition products. Moreover, the unevenness | corrugation of a sheet-like annealing separation material may be transcribe | transferred to a steel plate during annealing at high temperature, and may affect the shape of a steel plate.

On the other hand, Non-Patent Document 1 discusses a method of directly spraying a powdery annealing separator at a density of several tens of g / m ^{2 on} a steel sheet surface, not a sheet form, in the above-described method for producing a silicon steel sheet. . However, in this method, {100} textured silicon steel plate with stable and excellent magnetic properties, because the development of {100} texture is unstable and insufficient when large-scale steel sheets are laminated and coil annealed Is difficult to manufacture. In addition, industrially, a method of applying a powdered annealing separator on a steel plate as a slurry mixed with a liquid is most desired from the viewpoint of high productivity. However, in the method of applying and drying the slurry, a small size is required. There is a big problem that {100} texture does not develop at all even if it is a steel plate.

Japanese Patent Laid-Open No. 7-173542 JP-A-9-20966 International Publication No. WO 98/20179 JP 11-71617 A T. Tomida, N. Sano, K. Ueda, K. Fujiwara and N. Takahashi: J. Magn. Magn. Matter, 254-255, pp.315-317 (2003)

  The present invention has been made in view of the above problems, and can greatly reduce the cost. Further, even in the case of large-scale steel sheet lamination annealing and coil annealing, the magnetic properties are stable and excellent {100} The main object is to provide a method capable of producing a textured silicon steel sheet.

  As a result of earnest research on the application method of a slurry containing an annealing separator that is industrially desired, the present inventor has achieved a significant reduction in cost, and even in the case of large-scale steel sheet lamination annealing and coil annealing, the magnetic field is stable. A method for producing a {100} textured silicon steel sheet having excellent properties was found and the present invention was completed.

When applying and drying a slurry containing a powdered annealing separator, the amount of a general slurry applied is at most several tens of g / m ² . For this reason, also in the examination of the application of the slurry for developing the {100} texture, conventionally, the application amount has been in a range not exceeding the above tens of g / m ² .

On the other hand, in the present invention, the application of the slurry was examined at a coating amount far exceeding the conventional common sense range. As a result, even when using the method of applying the slurry, {100} aggregates can be obtained by applying a slurry containing appropriate annealing separator particles to the surface of the steel sheet at a weight of 80 g / m ² or more after drying. I found that the development of the organization is seen.

That is, the present invention contains C: 0.02% or more and 0.15% or less by mass%, and further contains Si and Mn within a range satisfying the following formulas (1) and (2). A slurry containing annealing separator particles made of at least one of a substance that promotes decarburization and a substance that promotes decarburization and de-Mn is applied to the surface of the steel plate at a weight of 80 g / m ² or more by dry mass. Manufacturing a {100} textured silicon steel sheet, comprising: a slurry application process for drying; and a final annealing process for subjecting the cold-rolled steel sheet coated with the slurry and dried to lamination annealing or coil annealing. Provide a method.
Si + Mn / 2 ≦ 5.0 (1)
Si-Mn / 2 ≧ 1.5 (2)
(Here, Si and Mn in the above formulas indicate the content (mass%) of each element.)

In the above invention, a substance that promotes the decarburization is material containing SiO _2, it is preferable substances which promote the above decarburization and de Mn of material containing TiO _2. This is because they are naturally produced in large quantities and are inexpensive.

At this time, the content of the SiO ₂ component and the TiO ₂ component in the annealing separator particles is preferably 10% by mass or more in total. This is because when the content of the SiO ₂ component and the TiO ₂ component is in the above range in total, a {100} texture can be developed in the final annealing and the magnetic flux density can be increased.

At this time, the substance containing SiO ₂ is preferably wollastonite. This is because the use of an inexpensive wollastonite acicular powder allows the {100} texture to be developed more efficiently and the cost to be greatly reduced.

  Under the present circumstances, it is preferable that content of the said wollastonite in the said annealing separator particle | grains is 20 mass% or more. This is because if the content of wollastonite is in the above range, a gap can be easily secured between adjacent cold-rolled steel plates with the slurry sandwiched during final annealing.

  Furthermore, in this invention, it is preferable that the said slurry contains 5 mass parts or less binder with respect to 100 mass parts of said annealing separator particles. This is because if a large amount of binder is contained in the slurry, a large amount of gas may be generated due to decomposition of the binder during the temperature increase of the final annealing.

  In the present invention, in the final annealing step, the space of the slurry after drying with respect to the space between the cold-rolled steel plates adjacent to each other with the slurry after drying sandwiched during the lamination annealing or the coil annealing. The packing density is preferably 50% by volume or less. This is because, if the space filling density of the slurry after drying is within the above range, the decarburization and deMn reaction in the final annealing can be further promoted, and the development of {100} texture can be further promoted.

  Furthermore, in this invention, it is preferable to apply | coat the said slurry to the surface of the said cold-rolled steel plate through the spacer provided with a hole. This is because a gap can be efficiently secured between the cold-rolled steel plates adjacent to each other with the slurry sandwiched in the final annealing.

  According to the present invention, since a predetermined amount or more of slurry containing predetermined annealing separator particles is applied to the surface of the cold-rolled steel sheet, a {100} texture can be developed in the final annealing step. There is an effect.

Hereafter, the manufacturing method of the {100} texture silicon steel plate of this invention is demonstrated in detail.
The method for producing a {100} texture silicon steel sheet of the present invention contains C: 0.02% or more and 0.15% or less by mass%, and further, Si and Mn are represented by the following formulas (1) and (2): On the surface of the cold-rolled steel sheet contained in a satisfactory range, after drying a slurry containing annealing separator particles composed of at least one of a substance that promotes decarburization and a substance that promotes decarburization and de-Mn It has a slurry application step of applying 80 g / m ² or more in mass and drying, and a final annealing step of subjecting the cold-rolled steel sheet coated with the slurry and dried to lamination annealing or coil annealing. Is.
Si + Mn / 2 ≦ 5.0 (1)
Si-Mn / 2 ≧ 1.5 (2)
(Here, Si and Mn in the above formulas indicate the content (mass%) of each element.)

According to the present invention, since the slurry containing the predetermined annealing separator particles is applied to the surface of the cold-rolled steel sheet at 80 g / m ² or more, which is a coating amount far exceeding the conventional common sense range, the final annealing is performed. In the process, {100} texture can be developed.
In the final annealing process, the entire steel plate is decarburized or decarburized and de-Mn is generated by lamination annealing or coil annealing, and the {100} plane parallel to the plate surface is increased by the γ → α transformation (austenite → ferrite transformation). A texture having a density can be developed. The γ → α transformation proceeds from the surface of the steel plate to the inside. The surface energy of crystal grains whose {100} plane is parallel to the plate surface is lower than the surface energy of crystal grains in other orientations. Therefore, it is considered that crystal grains whose {100} plane is parallel to the plate surface grow preferentially from the surface of the steel plate to the inside, and a texture having a high density of {100} planes parallel to the plate surface is obtained. .

In the present invention, a cold rolling process for producing a cold rolled steel sheet having the above steel composition is usually performed before the slurry application process.
Hereafter, each process of the manufacturing method of the {100} texture silicon steel plate of this invention is demonstrated.

1. Cold rolling process A cold rolling process is a process of producing the cold rolled steel plate which has the above-mentioned steel composition. Hereinafter, the steel composition and cold rolling of the cold rolled steel sheet will be described.

(1) Steel composition of cold-rolled steel sheet The cold-rolled steel sheet used in the present invention contains C: 0.02% or more and 0.15% or less by mass%, and Si and Mn are represented by the following formula (1) And it contains in the range which satisfies (2) Formula.
Note that “%” indicating the content of each element means “% by mass” unless otherwise specified.

(I) Si and Mn
Si and Mn are the most important components in terms of structure formation, magnetic properties, and workability in the final annealing.
The contents of Si and Mn are set to the following ranges in order to control the workability and phase state of the material in the manufacturing process.
Si + Mn / 2 ≦ 5.0 (1)
Si-Mn / 2 ≧ 1.5 (2)
(Here, Si and Mn in the above formulas indicate the content (mass%) of each element.)

  If Si + Mn / 2 exceeds 5.0, the steel sheet becomes brittle and cold rolling becomes difficult. Si + Mn / 2 is preferably 4.5 or less. On the other hand, if the Si-Mn / 2 is less than 1.5, the α phase (ferrite phase) becomes excessively unstable at high temperatures, so the intermediate annealing in cold rolling and the final annealing temperature must be reduced excessively. Rather, it makes organization formation difficult. Si-Mn / 2 is preferably 1.8 or more, more preferably 2.0 or more.

  The inclusion of Si and Mn is also effective for increasing the electric resistance value and reducing eddy current loss. Further, the inclusion of Mn promotes the formation of a {100} structure by causing removal of Mn in the final annealing. Therefore, the Mn content is preferably 0.4% or more, more preferably 0.6% or more, within the range satisfying the above formula.

(Ii) C
In order to perform structure control using decarburization in the final annealing, C is included in advance in the cold-rolled steel sheet used for the final annealing.
In order to sufficiently control the structure in the final annealing, the lower limit of the C content is 0.02% or more, preferably 0.03% or more. The upper limit of the C content is that the temperature range of the γ phase (austenite phase) at high temperature is excessively expanded, the annealing temperature must be excessively decreased, and the final annealing time required for sufficient decarburization is excessively long. In order to prevent this, and further to prevent the steel sheet from becoming brittle and difficult to roll the cold rolled material, it is set to 0.15% or less, preferably 0.1% or less, more preferably 0.08% or less.

(Iii) Solid solution Al
For the purpose of ensuring the soundness of the slab at the time of casting or fixing N, Al may be contained as necessary. However, when a large amount of Al is contained, selective oxidation of Al occurs on the steel sheet surface during final annealing, and there is a risk of inhibiting the development of {100} texture. Therefore, the Al content is preferably 0.005% or less, More preferably it is 0.002% or less, and still more preferably 0.001% or less.

(Iv) P
Generally, P is an impurity mixed in about 0.01% in the steel making stage, but has a function of increasing the strength of the steel sheet and improving the punchability. However, if P is contained in a large amount, the formation of {100} texture may be inhibited. Therefore, the P content is preferably 0.05% or less, more preferably 0.02% or less.

(V) Cr
Generally, Cr is an impurity mixed in about 0.02% in the steelmaking stage. Cr is dissolved in α-ferrite and has an effect of increasing electric resistance, so Cr may be contained. However, Cr has a strong tendency to generate carbides, and if it contains a large amount of Cr, there is a possibility that decarburization in the final annealing is delayed. Therefore, the Cr content is preferably 0.5% or less, more preferably 0.1% or less.

(Vi) Ni
In general, Ni is an impurity mixed in about 0.02% in the steelmaking stage. Ni may be contained because it dissolves in α-ferrite and increases electric resistance. However, when Ni is contained in a large amount, there is a possibility that the formation of {100} texture is hindered. For this reason, the Ni content is preferably 0.3% or less, more preferably 0.1% or less.

(Vii) Co
Co has an effect of increasing the saturation magnetic flux density and may be contained. However, since Co is expensive and has an effect of increasing magnetostriction, the Co content is preferably 1% or less.

(Viii) S
S may be contained because it has the effect of reducing the surface energy of the {100} plane during final annealing and promoting the development of the {100} texture. However, if S is contained in a large amount, MnS is precipitated in a large amount, which may inhibit the development of {100} texture. Therefore, the S content is preferably 0.005% or less, more preferably 0.003% or less.

(Ix) Sb
Sb may be contained because it has the effect of reducing the surface energy of the {100} plane during final annealing and promoting the development of the {100} texture. However, when a large amount of Sb is contained, there is a possibility that the development of {100} texture is inhibited. Therefore, the Sb content is preferably 0.03% or less.

(X) Other components In addition, impurities that are inevitably mixed may deteriorate workability or magnetic properties, so it is preferable that the amount be as small as possible.

(2) Cold rolling A cold rolling process will not be specifically limited if it is a process of producing the cold rolled steel plate which has the above-mentioned steel composition. The cold rolling step may be a step of performing one cold rolling, or may be a step of performing a plurality of cold rollings with intermediate annealing interposed therebetween. Among them, in order to develop a {100} <021> type {100} texture in the final annealing, it is preferable to perform one cold rolling without intervening the intermediate annealing. On the other hand, in order to develop a {100} <001> type {100} texture in the final annealing, it is preferable to perform a plurality of cold rollings with intermediate annealing.

  For cold rolling, a general method can be used, and conditions such as temperature and reduction ratio are appropriately selected depending on the steel composition, desired plate thickness, desired {100} texture, and the like.

  Above all, 50% or more to ensure fine structure and surface flatness to sufficiently develop {100} texture during final annealing, and to ensure sufficient plate thickness accuracy as iron core material It is preferable to perform cold rolling at a reduction ratio of. In particular, in order to develop a {100} <021> type {100} texture, it is preferable to perform cold rolling at a rolling reduction of 80% or more without interposing intermediate annealing.

  In addition, the reduction ratio in the case of performing cold rolling a plurality of times with intermediate annealing is the difference between the thickness of the steel sheet used for the first cold rolling and the thickness of the steel sheet after the final cold rolling. The value divided by the thickness of the steel sheet to be subjected to cold rolling.

  Moreover, a general method can be used for intermediate annealing, and conditions, such as temperature, are suitably selected by steel composition etc.

  In the present invention, it is not necessary to set an upper limit on the product plate thickness from the viewpoint of crystal structure. However, if the product plate thickness is excessively thick, it takes a long time for decarburization in the final annealing, and the eddy current loss of the product may increase. Therefore, the product plate thickness is preferably 0.5 mm or less. On the other hand, the lower limit of the product sheet thickness is not particularly limited as long as it can be manufactured by cold rolling.

  It does not specifically limit as a manufacturing method of the raw material used for cold rolling. As a raw material used for cold rolling, a cast ingot, a slab by continuous casting, a thin cast piece by strip casting, or a material obtained by hot rolling them can be used. From the viewpoint of improving productivity and ensuring surface flatness as a cold rolled material, it is preferable to use a hot rolled steel strip as the cold rolled material.

2. Slurry coating step The slurry coating step in the present invention comprises annealing separator particles comprising at least one of a substance that promotes decarburization and a substance that promotes decarburization and de-Mn on the surface of the cold-rolled steel sheet. This is a step of applying a slurry of 80 g / m ² or more in terms of the mass after drying and drying.
Hereinafter, the slurry, the slurry application method, and the slurry drying method will be described.

(1) Slurry The slurry used in the present invention contains annealing separator particles composed of at least one of a substance that promotes decarburization and a substance that promotes decarburization and de-Mn. Moreover, it is preferable that a slurry contains a binder.
Hereinafter, the annealing separator particles, the binder, and other components of the slurry will be described.

(I) Annealing Separator Particles The annealing separator particles used in the present invention are composed of at least one of a substance that promotes decarburization and a substance that promotes decarburization and de-Mn. That is, the annealing separator particles may be composed only of a substance that promotes decarburization, may consist only of a substance that promotes decarburization and de-Mn, and are a substance that promotes decarburization. Further, it may be made of a substance that promotes decarburization and de-Mn.

Among these, it is preferable that the annealing separator particles are composed of both a substance that promotes decarburization and a substance that promotes decarburization and de-Mn. Oxygen (O) generated from a substance that promotes decarburization may oxidize Mn in the steel sheet and degrade the surface properties. Therefore, when a substance that promotes decarburization and de-Mn is used in combination with a substance that promotes decarburization, Mn, which is a γ (austenite) stabilizing element, decreases from the surface layer of the steel sheet, so the γ → α transformation (austenite → ferrite Transformation) and oxidation of Mn can be suppressed. Moreover, when oxidation of Mn is suppressed, Mn which is not oxidized activates the surface of the steel sheet, so that the decarburization reaction can be promoted. Further, de-Mn can be applied to promote the γ → α transformation on the steel sheet surface.
The combined use of a substance that promotes decarburization and a substance that promotes deMn is described in detail in JP-A-7-73524.
Hereinafter, the substance that promotes decarburization, the substance that promotes decarburization and de-Mn, and other points of the annealing separator particles will be described.

(Substance that promotes decarburization)
The substance for promoting decarburization used in the present invention decomposes at the annealing temperature in the final annealing to generate oxygen, or is easily reduced by the carbon in the steel at the annealing temperature in the final annealing. Any substance that promotes charcoal is not particularly limited. Examples of the substance that promotes such decarburization include a substance containing Si oxide (SiO ₂ ).

The decarburization promoting action when SiO ₂ is used as an annealing separator is considered to be due to the following mechanism.
That is, the Si oxide is stable at room temperature, but becomes unstable when the temperature reaches about 1000 ° C., decomposition occurs as shown in the following formula (3), and oxygen is generated.
SiO ₂ → Si + 2O (3)
As shown in the following formula (4), this oxygen reacts with carbon in the steel to form carbon monoxide, resulting in decarburization.
O + C (solid solution in steel plate) → CO (gas) (4)
Summarizing the reactions of the formulas (3) and (4), the reaction of the following formula (5) is obtained.
SiO ₂ + 2C (solid solution in steel plate) → Si (in steel plate) + 2CO (gas) (5)

As a substance for promoting decarburization, in addition to a substance containing SiO ₂ , a suitable atmosphere at a high temperature such as Cr ₂ O ₃ , TiO ₂ , FeO, V ₂ O ₃ , V ₂ O ₅ , VO, MnO, etc. And materials containing oxides that are relatively unstable.

The “substance containing an oxide” may be composed of only the above oxide, or may be composed of the above oxide and another compound. For example, the “substance containing SiO ₂ ” may be composed only of SiO ₂ or may be composed of SiO ₂ and other compounds. Further, for example, the “substance containing TiO ₂ ” may be composed of only TiO ₂ or may be composed of TiO ₂ and other compounds.

  Note that the substance containing the above oxide “consists of the above oxide and another compound” means that the substance containing the above oxide is physically mixed with the above oxide and another compound. This means not only the case where the above oxide is a compound but also the case where the above-mentioned oxide is combined with another compound.

When the substance containing the above oxide is composed of the above oxide and another compound, examples of the other compound include the above oxide. In this case, the substance containing the oxide is composed of two or more kinds of the oxides. In addition, examples of the other compounds include inorganic substances that are stable at high temperatures, and examples thereof include oxides such as Al ₂ O ₃ , CaO, and MgO, nitrides such as BN, and carbides such as SiC. In this case, the substance containing the oxide is composed of the oxide and the inorganic substance.

Among the materials described above, the material containing SiO ₂ and the material containing TiO ₂ are most preferable as the material for promoting decarburization. Substances containing these oxides are naturally produced in large quantities and are inexpensive. As will be described later, since the substance containing TiO ₂ also promotes de-Mn, the substance containing TiO ₂ can be used alone to promote both decarburization and de-Mn.

When the annealing separator particles contain at least one of a substance containing SiO ₂ and a substance containing TiO ₂ , the content of the SiO ₂ component and the TiO ₂ component in the annealing separator particles is 10% by mass or more in total. Preferably, it is 25 mass% or more, more preferably 50 mass% or more. This is because when the content of the SiO ₂ component and the TiO ₂ component is in the above range in total, a {100} texture can be developed in the final annealing and the magnetic flux density can be increased.

As mentioned above, substances containing SiO ₂ are naturally produced. Examples of the naturally-occurring substance containing SiO ₂ include natural minerals such as quartzite, quartz sand, diatomaceous earth, kaolinite, molocite, talc, and wollastonite. Among these, wollastonite that easily becomes a needle-like powder by cleavage is most preferable. This is because the acicular powder can easily form voids in the dried slurry. After applying and drying the slurry on the surface of the cold rolled steel sheet, final annealing is performed in a state where the slurry and the cold rolled steel sheet are alternately laminated. In order to promote the decarburization and deMn reaction in the final annealing, it is preferable that an appropriate gap exists between the cold-rolled steel plates adjacent to each other with the slurry interposed therebetween. That is, it is preferable that voids are formed in the slurry. The voids between the cold-rolled steel sheets improve the air permeability necessary for decarburization and de-Mn, promote the decarburization and de-Mn reaction in the final annealing, and promote the development of {100} texture.
Here, wollastonite (WOLLASTNITE) is represented by the chemical formula CaO.SiO ₂ .

When the annealing separator particles contain wollastonite, the content of wollastonite in the annealing separator particles is preferably 20% by mass or more, more preferably 25% by mass or more, and further preferably 50% by mass. That's it. This is because if the content of wollastonite is within the above range, voids can be more easily formed in the slurry after drying. On the other hand, the content of wollastonite is preferably 90% by mass or less. This is because it becomes possible to contain TiO ₂ in an amount of 10% by mass or more, thereby developing a {100} texture in the final annealing and increasing the magnetic flux density.

(Substance that promotes decarburization and de-Mn)
The substance that promotes decarburization and de-Mn used in the present invention decomposes at the annealing temperature in the final annealing to generate oxygen, or is easily reduced by carbon in the steel at the annealing temperature in the final annealing. If it is a substance that promotes decarburization and absorbs Mn sublimated from the steel plate during the final annealing and does not adversely affect the decarburization reaction or the surface energy state of the steel plate It is not particularly limited. Examples of the substance that promotes such decarburization and de-Mn include a substance containing Ti oxide (TiO ₂ ).
As described above, the “substance containing TiO ₂ ” may be composed only of TiO ₂ or may be composed of TiO ₂ and other compounds.

Mn in the steel sheet sublimes from the surface of the steel sheet under an appropriate atmospheric condition, whereby a Mn-depleted layer (de-Mn layer) is formed near the surface of the steel sheet. TiO ₂ is considered to promote de-Mn by forming Mn sublimated from the steel sheet and a composite oxide (TiMnO ₂ ) and absorbing Mn. TiO ₂ is a substance that also promotes decarburization. Therefore, TiO ₂ can be used alone to promote both decarburization and de-Mn.

Note that the content of the substance and TiO ₂ component containing TiO _2, since described in Materials for promoting the decarburization, and description thereof is omitted here.

(Annealing separator particles)
The form of the annealing separator particle in the present invention is not particularly limited as long as it is a particle (powder), but a fibrous powder is particularly preferable. The fibrous powder becomes strong after the slurry is dried by the addition of a small amount of binder to the slurry. Therefore, even when a cold-rolled steel sheet coated with the slurry is laminated or wound in a coil shape, the voids formed in the dried slurry are maintained without being crushed. As a result, voids are easily formed in the dried slurry.

  In the case where the annealing separator particles are composed of a plurality of types of particles, it is preferable that the form of at least one type of particles is a fibrous powder.

Moreover, the particle size of the annealing separator particles is not particularly limited, but is preferably about 0.05 μm to 500 μm, more preferably within the range of 0.1 μm to 200 μm. In the case where the annealing separator particles are composed of a plurality of types of particles, the particle size of each particle may be in the above range. If the particle size is less than the above range, the gap maintained between the cold-rolled steel plates adjacent to each other with the slurry therebetween becomes small, and the progress of the decarburization and de-Mn reaction may be slow, and the magnetic properties are This is because it may not improve. Conversely, if the particle size exceeds the above range, the annealing separator particles tend to settle during the preparation of the slurry, making it difficult to stably and uniformly apply the slurry to the surface of the cold rolled steel sheet. This is because there is a case. Further, if the particle diameter exceeds the above range, the annealing separator particles are pushed into the surface of the cold rolled steel sheet, the surface shape of the cold rolled steel sheet is impaired, and the magnetic properties may be impaired.
In the case where the annealing separator particles are composed of a plurality of types of particles, the particle size of each particle may be in the above range.
The particle size of the annealing separator particles can be measured by a laser diffraction method.

(Ii) Binder In the present invention, in order to prevent the annealing separator particles from being detached from the steel sheet after the slurry is dried, a void is formed in the slurry after drying, and the strength for retaining the void is increased. In order to ensure, it is preferable to add a binder to the slurry.

  As the binder, organic resins such as PVA, cellulose polymer, acrylic polymer, nylon polymer, and polyethylene polymer, and inorganic materials such as phosphoric acid can be used. Among these, an organic resin that decomposes at a relatively low temperature is preferable. This is because such an organic resin is not decomposed during the temperature increase of the final annealing and hardly affects the subsequent formation of the steel sheet structure.

  However, if a large amount of binder is contained in the slurry, a large amount of gas may be generated due to decomposition of the binder during the temperature increase of the final annealing. Therefore, the content of the binder in the slurry is the annealing separator particles. The amount is preferably 5 parts by mass or less, more preferably 3 parts by mass or less, and still more preferably 2 parts by mass or less with respect to 100 parts by mass. The lower limit of the content of the binder in the slurry is not particularly limited as long as it can ensure the strength to retain the voids in the slurry after drying, but is preferably 0.1 to 100 parts by mass of the annealing separator particles. More than part by mass.

(Iii) Additive In the present invention, when water is added to the slurry, a small amount of rust preventive may be added to the slurry in order to prevent oxidation of the steel sheet surface during application and drying of the slurry.
Moreover, you may add a thickener, a peptizer, a plasticizer, and a wetting improver to a slurry.

(Iv) Method for Preparing Slurry In the present invention, a slurry can be prepared by adding a liquid such as water or alcohol to the above-described annealing separator particles. Examples of the liquid used at this time include water and alcohol. Among them, water is preferable from the viewpoint of cost.

  When water is used, it is preferable to reduce dissolved oxygen in order to prevent oxidation of the steel sheet surface by dissolved oxygen in water and promote the development of {100} texture. The dissolved oxygen amount of water in the slurry is preferably 5 mg / l or less, more preferably 3 mg / l or less.

  Moreover, it is preferable that solid content in a slurry shall be about 50 mass%-80 mass%. When the solid content in the slurry is less than the above range, drying may take time. When the solid content in the slurry exceeds the above range, the slurry viscosity becomes too high and it is difficult to apply to the steel plate. It is because it may become.

(2) Slurry application method Slurry may be applied to one side of a cold rolled steel sheet, or may be applied to both sides of a cold rolled steel sheet. Among them, in order to promote the development of {100} texture Moreover, it is preferable to apply to one side of the cold rolled steel sheet.

The amount of slurry applied must be at least 80 g / m ² or more in terms of the mass after drying. If the application amount of the slurry is less than the above range, {100} texture development is insufficient in the central portion of the laminate or coil when the size of the cold-rolled steel sheet increases. The amount of slurry applied is preferably 100 g / m ² or more. If the amount of slurry applied is excessively large, the laminate or coil becomes large, and the amount of annealing separator particles used may be excessive and costly, so the upper limit of the amount of slurry applied is preferably It is 500 g / m ² or less, more preferably 300 g / m ² or less.

  As a slurry application method, a general application method using a rubber roll or the like can be employed. In particular, during final annealing, in order to efficiently secure a gap between adjacent cold-rolled steel plates with the slurry in between, a spacer having a hole such as a net having a proper aperture ratio or a plate with a hole is cooled. It is preferable to place on a rolled steel sheet and apply the slurry via the spacer. Thereby, a space | gap can be ensured naturally between the cold rolled steel plates adjacent on both sides of the slurry.

  When applying slurry continuously to a long cold-rolled steel sheet, the spacer is cylindrical or belt-shaped, and is rotated and moved in synchronization with the steel sheet feed speed. From the viewpoint of productivity, it is preferable to apply the slurry via the step. In this case, a roller, a squeegee, etc. can be used for application | coating of a slurry.

  The shape of the hole of the spacer is not particularly limited, and can be various shapes.

It is preferable that the space | interval of the hole part of a spacer is so small that an unevenness | corrugation is not transferred to a steel plate during the last annealing, and specifically, it exists in the range of 0.1 mm-2 mm.
In addition, the space | interval of a hole part means the distance from the center position of an adjacent hole part to a center position.

  Further, the opening ratio of the spacer is preferably in the range of 10% to 90%. When the opening ratio is less than the above range, the area ratio of the slurry covering the steel sheet is too small, and seizure may occur between the steel sheets. On the other hand, if the aperture ratio exceeds the above range, the void density in the slurry becomes small, which may inhibit the development of {100} texture.

(3) Drying method of slurry As a drying method of the slurry, natural drying may be used, but heating is preferable for shortening the time. In the case of heating, for example, an oven or a hot plate can be used.

  The drying temperature is room temperature in the case of natural drying. On the other hand, when heating is performed and water is added to the slurry, the drying temperature is preferably set in the range of 50 ° C to 100 ° C. This is because it is preferable to complete the drying within a few minutes after applying the slurry from the viewpoint of preventing the surface oxidation of the steel sheet.

Further, the atmosphere during drying may be an air atmosphere or an inert gas atmosphere. In particular, when heating is performed at the time of drying, and when water is added to the slurry, an N ₂ atmosphere is preferable. At this time, it is preferable to heat in an N ₂ stream. As described above, it is preferable to complete the drying within several minutes after applying the slurry from the viewpoint of preventing the surface oxidation of the steel sheet.

(4) Others In the present invention, when water is added to the slurry, a rust preventive film or a hydrophobic film is previously formed on the steel sheet surface in order to prevent oxidation of the steel sheet surface during application / drying of the slurry. It may be left.

3. Final annealing step The final annealing step in the present invention is a step of subjecting the cold-rolled steel sheet coated with the slurry and dried to lamination annealing or coil annealing.
By this final annealing, both decarburization or decarburization and de-Mn are generated, and a texture having a high density of {100} planes parallel to the plate surface is developed by the γ → α transformation generated in this process, The carbon content can be sufficiently reduced. The γ → α transformation proceeds sequentially from the surface of the steel plate to the inside. Since the surface energy of crystal grains whose {100} plane is parallel to the plate surface is much lower than the surface energy of crystal grains in other orientations, the crystal grains whose {100} plane is parallel to the plate surface are preferential. It is thought that the texture grows from the surface to the inside of the steel plate and develops a texture with a high density of {100} faces parallel to the plate surface.

  The cold-rolled steel sheet to which the slurry is applied and dried is annealed in a state where the dried slurry and the cold-rolled steel sheet are alternately laminated. When the cold-rolled steel sheet is long, it is preferable to anneal the cold-rolled steel sheet coated with the slurry and wound in a coil shape. This is coil annealing. When the cold-rolled steel sheet is short, another cold-rolled steel sheet not coated with the slurry is laminated on the cold-rolled steel sheet coated with the slurry or dried, or the cold-rolled steel sheet coated with the slurry and dried. Annealing is preferably performed in a state where a plurality of intermediate rolled steel plates are laminated. This is lamination annealing.

  In the final annealing, when the cold-rolled steel sheet coated with the slurry and dried is in a state where the dried slurry and the cold-rolled steel sheet are alternately laminated as described above, the dried slurry is adjacent to each other. It is preferable that a gap exists between the cold rolled steel sheets. The space filling density of the slurry after drying is preferably 50% by volume or less, more preferably 35% by volume or less with respect to the space between the cold-rolled steel plates adjacent to each other with the slurry after drying. This is because, if the space filling density of the slurry after drying is within the above range, the decarburization and deMn reaction in the final annealing can be further promoted, and the development of {100} texture can be further promoted. On the other hand, the lower limit of the space filling density of the slurry after drying is preferably 5% by volume or more. If it is less than the above range, seizure tends to occur between the steel plates.

In addition, space filling density means the ratio of the volume of the slurry after drying which occupies the whole space (volume) between the cold-rolled steel plates adjacent on both sides of the slurry after drying.
This space filling density is determined as (m / ρ) / d from the average weight d of the laminated steel sheets and the dry weight m per unit surface area of the slurry and the average density ρ after drying of the slurry.

  Examples of a method for causing a gap between adjacent cold-rolled steel plates with the slurry sandwiched between them are a method of adjusting the particle size (particle size) and form of the annealing separator particles, and a slurry is applied via a spacer having a hole. And a method of forming bubbles by mixing a foaming agent in the slurry.

  The annealing atmosphere is preferably an atmosphere mainly composed of hydrogen, an inert gas, or a mixed gas of hydrogen and an inert gas, or a vacuum.

  In the case of a vacuum atmosphere, the pressure is preferably 100 Torr or less, more preferably 1 Torr or less. This is because if the pressure exceeds the above range, the {100} surface density may decrease.

  The holding temperature during annealing is desirably 1300 ° C. or lower. An annealing temperature exceeding 1300 ° C is difficult to achieve industrially. Since the decarburization reaction proceeds faster as the temperature increases, the holding temperature is preferably 950 ° C. or higher, more preferably 1050 ° C. or higher for efficient decarburization. The most preferable temperature for remarkable development of {100} texture and more efficient decarburization is the α + γ two-phase coexisting temperature range of 1050 ° C to 1150 ° C.

  The soaking time during annealing is preferably in the range of 30 minutes to 100 hours. This is because if the holding time is less than the above range, decarburization and de-Mn will be insufficient, while if the holding time exceeds the above range, productivity may be deteriorated.

4). Other Steps In the present invention, usually, an annealing separator particle step for removing the annealing separator particles from the steel sheet is performed after the final annealing step.
Examples of the method for removing the annealing separator particles include washing with water.

Moreover, in this invention, in order to ensure the electrical insulation between each steel plate at the time of laminating | stacking and using a steel plate after the said annealing separating agent particle process, the surface coating process which apply | coats an insulating film on the steel plate surface can be performed. preferable.
Insulating coatings include inorganic insulating coatings in which a phosphate-based or Cr-based inorganic solution is applied to a steel plate and baked, or a mixture of this inorganic solution and an organic resin such as a polyacrylic emulsion. An organic-inorganic mixed film that is applied and baked on the substrate is mentioned.

5). {100} Textured silicon steel sheet The {100} textured silicon steel sheet produced according to the present invention is not particularly limited as long as it has a {100} texture, but {100} <100> texture ({100} <100> type {100} texture) or {100} <021> texture ({100} <021> type {100} texture). Steel plates with {100} <100> texture show excellent magnetic properties in two directions, the rolling direction and the sheet width direction, and steel plates with {100} <021> texture are in all directions within the rolling surface. This is because the magnetic characteristics are almost equal to.

For steel plates with {100} <100> texture, grains with an orientation within ± 15 ° from the {100} <100> orientation are 70% or more of the observation plane (cross section parallel to the plate surface), especially 80% It is preferable to occupy the above.
In addition, the orientation within ± 15 ° from the {100} <100> orientation means that the angle between the <100> axis closest to the rolling direction of the crystal grain steel plate and the rolling direction is a, and the steel plate of the crystal grain steel plate When the angle between the <100> axis closest to the width direction and the plate width direction is b, the average [(a + b) / 2] of these is within 15 °.

In addition, in the case of a steel plate having a {100} <021> texture, crystal grains with an orientation within ± 15 ° from the {100} <021> orientation are 70% or more of the observation surface (cross section parallel to the plate surface), It is preferable to occupy 80% or more.
Note that the orientation within ± 15 ° from the {100} <021> orientation means that the angle between the <021> axis closest to the rolling direction of the grain steel plate and the rolling direction is c, and the grain steel plate When the angle formed between the <021> axis closest to the width direction and the plate width direction is d, the average [(c + d) / 2] is within 15 °.

  Further, the C content of the steel sheet after the final annealing step is preferably less than 0.005%, more preferably 0.003% or less, and further preferably 0.002% or less in order not to deteriorate the magnetic properties. This is because C remaining beyond the solid solubility limit in α-ferrite precipitates as cementite in α-ferrite and deteriorates magnetic properties.

  The present invention is not limited to the above embodiment. The above-described embodiment is an exemplification, and the present invention has any configuration that has substantially the same configuration as the technical idea described in the claims of the present invention and that exhibits the same effects. Are included in the technical scope.

Hereinafter, the present invention will be described specifically by way of examples and comparative examples.
[Example 1]
A steel having the steel composition shown in Table 1 below was cast in a vacuum, hot forged, and then hot rolled to a thickness of about 3 mm. Further, the hot-rolled steel sheet was pickled to remove oxides, and then cold-rolled to a thickness of about 0.9 mm and annealed at 1050 ° C. for 30 seconds. The steel sheet was cold-rolled again to a thickness of 0.35 mm to remove the rolling oil, and then subjected to the following annealing experiment.

It was prepared by mixing the annealing separator particles 1: and SiO ₂ powder having an average particle size of about 40 [mu] m, and a TiO ₂ powder following anatase structure particle size 1μm at a weight ratio 1. A slurry was prepared by adding water in which PVA and a peptizer were dissolved to the annealing separator particles. The dissolved oxygen content of water in the slurry was 2 mg / l. The amount of PVA added was about 2 parts by mass with respect to the total mass (100 parts by mass) of the annealing separator particles.

  This slurry was applied to one side of a 250 mm × 300 mm square cold-rolled steel sheet through a spacer having an aperture ratio of 50% and a hole with a diameter of 0.8 mm at various coating amounts shown in Table 2 below, and then around 90 ° C. And dried. Ten such steel plates were prepared, and they were laminated so that the steel plates in contact with the adjacent steel plates were contacted via the slurry after drying, and so that the steel plates having the same coating amount were continuous. The packing density of the slurry after drying between the adjacent steel plates across the dried slurry was about 33% by volume.

This laminate was charged into a vacuum furnace, evacuated to a pressure of 10 ⁻⁴ Torr, heated to 1100 ° C. at a rate of 1 ° C./min, and soaked for 12 hours. The annealing separator particles were removed from the annealed steel sheet, and strip test pieces of 280 mm × 30 mm were cut out along the rolling direction or the sheet width direction. After annealing at 900 ° C. for 1 hour in order to remove the strain, the magnetic properties in the rolling direction and the plate width direction of these steel plates were measured using a single plate magnetization measuring device. The measurement frequency was 50 Hz. Also, the texture is measured using EBSP (Electron Back Scattering Pattern) to determine the type of texture that has developed, and if a specific texture has developed, the orientation within 15 ° from that orientation The volume of the held crystal grains was determined. The results are shown in Table 2. The carbon content after annealing of these steel sheets was 0.003% or less.

When the amount of slurry applied is small (test pieces No. 1 to 4), the {100} <001> texture is poorly developed, and a magnetic flux density of B ₁₀ (1000 A / m magnetic field was applied in the rolling direction and the plate width direction) It was found that the magnetic flux density at the time was small. On the other hand, when the application amount of the slurry exceeds 80 g / m ² (test pieces No. 5 to 13), {100} <001> texture develops significantly and B ₁₀ increases to 1.8T or more. It was found that a high-performance bi-directional silicon steel sheet was obtained.

  In addition, in order to investigate the flatness of the plate after annealing, the total thickness was measured by stacking 20 strip test pieces as described above, and the total thickness obtained by calculation from the specific gravity, mass, length and width of the steel plate was calculated. Dividing by the measured total thickness, the space factor of the board at the time of lamination was calculated. The space factor was 93% to 95% in all cases, and the flatness of the plate was good.

[Example 2]
A small amount of a rust inhibitor was applied in advance to a long coil (width 250 mm, length 100 m) of the same cold rolled steel plate as in Example 1 and subjected to the following annealing experiment.

30% by mass of TiO ₂ powder used in Example 1 and 70% by mass of wollastonite needle-like powder (about 35 aspect ratio) containing about 97% CaSiO ₃ (CaO + SiO ₂ ) were mixed for annealing separation. Agent particles were prepared. A small amount of water and peptizer in which methylcellulose and PVA were dissolved were added to the annealing separator particles to prepare a slurry. The dissolved oxygen content of water in the slurry was 1.5 mg / l. The total amount of methylcellulose and PVA was 1.5 parts by mass with respect to the total mass (100 parts by mass) of the annealing separator particles.

200 g / m ^{2 of} this slurry was applied to one side of the cold-rolled steel sheet through a spacer having a hole with an opening ratio of 45% that moves and renewed in synchronization with the surface of the steel sheet. After that, it was immediately heated to about 80 ° C. in a N ₂ stream and dried, and the cold rolled steel sheet was wound up in a coil shape. The packing density of the slurry after drying between adjacent steel plates across the dried slurry was about 27% by volume.

The coil was placed in a vacuum furnace, evacuated to a pressure of 10 ⁻³ Torr, heated to 1100 ° C. at a rate of 1 ° C./min, and soaked for 15 hours. The steel plate after annealing had a carbon content of 0.0015% and was sufficiently decarburized. These steel sheets were measured in the same manner as in Example 1. The results are shown in Table 3.

The magnetic flux density B ₁₀ in the rolling direction and the plate width direction is not less than 1.87T, bidirectional silicon steel high characteristics it was found that was obtained. It can also be seen from Table 3 that this depends on the development of {100} <001> texture.
When the plates were laminated, the space factor was 95% or more, and the flatness of the plates was even better than in the case of lamination annealing.

[Example 3]
A steel having the steel composition shown in Table 4 was cast in a vacuum and hot forged, and then hot rolled to a thickness of about 5 mm. Further, the hot-rolled steel sheet was pickled to remove oxides, and then cold-rolled to a thickness of about 0.35 mm, the rolling oil was removed with a solvent, and the following annealing experiment was performed.

SiO ₂ powder having a purity of about 99% and a particle size of 100 μm or less, Al ₂ O ₃ powder having a purity of about 99%, a TiO ₂ powder having an anatase type crystal structure having a purity of about 99% and a particle size of 1 μm or less, and CaSiO ₃ ( Wollastonite ore-like powder containing about 97% CaO + SiO ₂ ), diatomaceous earth containing 88% SiO ₂ and 7% Al ₂ O _3, and containing 52% SiO ₂ and 43% Al ₂ O ₃ Molocite powder and rutile sand containing about 96% of TiO ₂ having a rutile crystal structure were prepared. These were mixed in the amounts shown in Table 5 below to prepare mixed powders. The mixed powder was further added with water in which an acrylic polymer was dissolved to prepare a slurry. The dissolved oxygen content of water in the slurry was 4.5 mg / l. The addition amount of the acrylic polymer was 0.5 to 10 parts by mass with respect to the total mass (100 parts by mass) of the mixed powder.

This slurry was applied to one side of a cold-rolled steel sheet at a dry mass of 200 g / m ² and then heated to around 90 ° C. and dried in a N ₂ stream. Next, 10 such steel plates were produced, and they were laminated so that the steel plates in contact with the adjacent steel plates were in contact with each other through the dried slurry, and the steel plates having the same slurry conditions were continuous. The packing density of the slurry after drying between adjacent steel plates with the slurry after drying in the range of 30% to 35% by volume.

This laminate was charged into a vacuum furnace, evacuated to a pressure of 10 ⁻⁴ Torr, heated to 1125 ° C. at a rate of 1 ° C./min, and soaked for 5 hours. The annealing separator particles were removed from the steel plates after annealing, and ring-shaped test pieces having an outer diameter of 50 mm and an inner diameter of 35 mm were punched from these steel plates. Thereafter, strain relief annealing was performed at 900 ° C. for 1 hour, ring-shaped test pieces were stacked, primary and secondary coils for magnetization measurement were wound, and magnetic characteristics were measured at a frequency of 50 Hz. In addition, the texture is measured using EBSP (Electron Back Scattering Pattern) to determine the form of the texture that has developed, and if a specific texture is developed, it has an orientation within 15 ° from that orientation. The volume of the crystal grains was determined. The carbon content of the steel sheet after annealing was also investigated. The results are shown in Table 6.

It was found that when no decarburization or de-Mn promoting substance was contained and only Al ₂ O ₃ was contained (test piece No. a), decarburization did not occur and the carbon content was hardly reduced. In this case, the {100} texture does not develop, and the magnetic flux density B ₁₀ (magnetic flux density when a magnetic field of 1000 A / m is applied) of the characteristics using the ring-shaped test piece (average characteristics in the plate surface) is It became small with 1.35T. On the other hand, in the present invention example (test pieces No. b to f) containing substances that promote decarburization and de-Mn, the carbon content is sufficiently reduced by decarburization and {100} <021> texture develops and, the magnetic flux density B ₁₀ is increased. In addition, among the examples of the present invention, when the acrylic polymer was added as much as 10% (test piece No. f), the development of {100} <021> texture tended to be slightly worse.
The space factor during lamination was 92% to 95% in all cases, and the flatness of the plate was good.

It is a figure which shows a crystal orientation typically.

Claims (8)

The content of C: 0.02% or more and 0.15% or less by mass%, and Si and Mn in the range satisfying the following formulas (1) and (2) are removed on the surface of the cold rolled steel sheet. Slurry coating process in which a slurry containing annealing separator particles composed of at least one of a substance that promotes charcoal and a substance that promotes decarburization and de-Mn is applied at a dry mass of 80 g / m ² or more and dried. When,
And a final annealing step of subjecting the cold-rolled steel sheet coated with the slurry and dried to lamination annealing or coil annealing. A method for producing a {100} texture silicon steel sheet.
Si + Mn / 2 ≦ 5.0 (1)
Si-Mn / 2 ≧ 1.5 (2)
(Here, Si and Mn in the above formulas indicate the content (mass%) of each element.) The {100} assembly according to claim 1, wherein the substance that promotes decarburization is a substance containing SiO _2, and the substance that promotes decarburization and deMn is a substance containing TiO _2. A method for producing a structured silicon steel sheet. _{3. The} method for producing a {100} texture silicon steel sheet according to claim 2, wherein the content of the SiO ₂ component and the TiO ₂ component in the annealing separator particles is 10% by mass or more in total. The method for producing a {100} texture silicon steel sheet according to claim 2 or 3, wherein the substance containing SiO ₂ is wollastonite.   5. The method for producing a {100} texture silicon steel sheet according to claim 4, wherein the wollastonite content in the annealing separator particles is 20% by mass or more.   The said slurry contains 5 mass parts or less binder with respect to 100 mass parts of said annealing separator particles, The {100} texture silicon in any one of Claim 1-5 characterized by the above-mentioned. A method of manufacturing a steel sheet.   In the final annealing step, during the lamination annealing or the coil annealing, the space filling density of the slurry after drying is 50% by volume with respect to the space between the cold-rolled steel plates adjacent to each other with the slurry after drying interposed therebetween. The method for producing a {100} texture silicon steel plate according to any one of claims 1 to 6, wherein:   The method for producing a {100} texture silicon steel plate according to claim 7, wherein the application of the slurry to the surface of the cold-rolled steel plate is performed through a spacer having a hole.

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