JPH11307333A - Electromagnetic steel plate with superior sticking resistance and corrosion resistance - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an electromagnetic steel plate having superior sticking resistance and corrosion resistance, and other superior characteristics required as an insulating film. SOLUTION: This electromagnetic steel plate is provided with an insulating film, whose film thickness is 0.2-2.0 μm formed by applying processing liquid obtained by mixing organic resin emulsion (b1) made of one kind or two or more kinds of specific resin emulsion whose resin grain diameter is 0.2 μm or less and organic resin emergent (b2) made of one kind of two or more kinds of specific resin emulsion whose grain diameter is 0.3-2.5 μm with inorganic aqueous solution (a) containing at least one kind selected from among anhydrous chromic acid, chromate, and bichomate, and at least one kind selected from among bivalent or trivalent metal oxide, hydroxide, carbonate, and mixing nitric acid and/or nitrate with organic reducing agent as necessary to the surface of this electromagnetic steel plate, and burning this.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electromagnetic steel sheet having an insulating film on its surface, which is mainly used as an iron core material for motors and transformers.

[0002]

2. Description of the Related Art Magnetic steel sheets are widely used as iron core materials for motors and transformers, and are usually used by coating an insulating film on the steel sheet surface to reduce eddy current loss. Many iron cores, such as motors and transformers, are manufactured by punching or shearing electromagnetic steel sheets on which an insulating film is formed into a predetermined shape and then laminating them.The laminate is fixed by welding or caulking, and strain is removed as necessary. After annealing, the product is obtained by winding the wire.

[0003] In addition to having high insulation properties, the insulation film of an electromagnetic steel sheet, which is a material for such an iron core, has high film adhesion,
It is required to be excellent in weldability, corrosion resistance, punching property and the like. Further, when the strain relief annealing is performed, when the steel sheets adhere to each other (sticking) during the annealing, an electric short circuit occurs and a problem that the iron loss increases, so that the steel sheets do not adhere during the annealing, that is, Excellent sticking resistance is required.

Conventionally, the following techniques have been proposed to obtain such various characteristics. JP-A-3-24097
No. 0 describes chromic acid as a method for producing electrical steel sheets with excellent film properties (seizure resistance and lubricity) after strain relief annealing.
Oxides such as Al and Mg, and a resin particle diameter of 0.2 to 0.5;
μm organic resin emulsion (acrylic, styrene, vinyl acetate and / or copolymer resin thereof) and organic resin emulsion having a resin particle diameter of 1 to 50 μm (resin such as methyl methacrylate, polyacrylonitrile, polystyrene and / or the like) There is disclosed a method of forming an insulating film by applying a treatment liquid composed of these copolymer resin and crosslinked resin) to the surface of an electromagnetic steel sheet and baking it.

[0005] Japanese Patent No. 2662148 discloses that one type of epoxy, styrene, phenol, melamine, polyester, vinyl acetate, acrylic, or silicone emulsion resin having a resin particle size of 0.5 to 3.0 μm is coated on the surface of an electromagnetic steel sheet. Two or more types and a treating agent mainly containing one or more types of chromates of Al, Mg, Ca, and Zn are applied and baked, and the insulation having a surface roughness Ra of 0.15 to 0.6 μm is obtained. A film is formed, and a spherical projection formed on the surface by the emulsion resin has a diameter of 3 μm or less and a height of 3 μm.
A non-oriented electrical steel sheet having excellent film properties of not more than m is shown.

[0006]

However, these prior arts have the following problems. JP-A-3-2409
The technology of No. 70 is based on an organic resin emulsion in which, in addition to resin fine particles having a particle size of 0.2 to 0.5 μm, coarse resin particles having a large particle size (substantially several μm or more) are obtained to obtain a predetermined surface roughness. Resin particles having a particle diameter). For this reason, although the sticking resistance is improved by the added coarse resin particles, the corrosion resistance in a severe corrosive environment where chloride ions are present is inferior. Further, there is also a problem that the film characteristics are not stable due to the aggregation of the resin particles due to the addition of the coarse resin particles and the unevenness of the resin particles in the film.

The technology disclosed in Japanese Patent No. 2662148 is
0.5 to 3 to give the insulating film a predetermined surface shape.
Although the organic resin emulsion having a particle size of 0 μm is used alone, when the thickness of the insulating film becomes a thin film of 0.5 to 0.6 μm or less, the resin particles are missing and hardly contained in the film, As a result, the effect of anti-sticking properties expected from the resin particles is reduced, rust is easily generated in the missing portion, and the corrosion resistance is extremely poor. In particular, in recent years, insulating films have tended to be thinner from the viewpoint of increasing the efficiency of motors and the like. In such thin film insulating films, the technique of Patent No. 2662148 does not provide sufficient sticking resistance and corrosion resistance. I can't get it.

Accordingly, an object of the present invention is to provide an electrical steel sheet having an insulating film excellent in both sticking resistance and corrosion resistance and also having other properties required as an insulating film, especially, 0.5 to 0.5 mm. An object of the present invention is to provide an electromagnetic steel sheet that can obtain excellent sticking resistance and corrosion resistance even when a thin insulating film having a thickness of 6 μm or less is formed.

[0009]

Means for Solving the Problems The present inventors focused on the resin particle diameter of an organic resin emulsion blended with an inorganic component when forming an inorganic-organic insulating film, and found that both the sticking resistance and the corrosion resistance were good. Various experiments and examinations were conducted on the conditions for obtaining an excellent insulating film, and as a result, the following findings were obtained.

(1) The sticking resistance is improved by increasing the resin particle diameter of the organic resin emulsion dispersed in the insulating film, but the corrosion resistance is degraded as the resin particle diameter increases. (2) To solve such a problem, as an organic resin emulsion dispersed in an insulating film, a composite of a fine particle organic resin emulsion having a specific particle size and an organic resin emulsion having a specific particle size larger than this is used. By adding, an insulating film excellent in both sticking resistance and corrosion resistance can be obtained.

(3) In addition, when these two kinds of organic resin emulsions to be added in combination are blended at a specific ratio, particularly excellent sticking resistance and corrosion resistance can be obtained. (4) By optimizing the ratio of the inorganic component to the organic component in the insulating film and adding boric acid and / or borate as a part of the inorganic component, the sticking resistance and the corrosion resistance are further improved. The present invention has been made based on such knowledge, and has the following configuration.

[1] Chromic anhydride,
An inorganic aqueous solution containing at least one selected from chromates and dichromates and at least one selected from oxides, hydroxides and carbonates of divalent or trivalent metals (a ) And one selected from resin emulsions of epoxy resin, styrene resin, phenol resin, melamine resin, polyester resin, vinyl acetate resin, veova resin, acrylic resin, and silicone resin. Or an organic resin emulsion (b1) composed of two or more kinds and having a resin particle diameter of less than 0.2 μm, an epoxy resin, a styrene resin, a phenol resin, a melamine resin, a polyester resin, a vinyl acetate resin, One or more resin emulsions selected from veova-based resin, acrylic-based resin, and silicone-based resin emulsion, and having a resin particle diameter of 0.3 to 2 Sticking resistance, characterized in that it has an insulating film having a thickness of 0.2 to 2.0 μm formed by applying and baking a treatment liquid containing an organic resin emulsion (b2) of 5 μm as a main component and Electrical steel sheet with excellent corrosion resistance.

[2] Chromic anhydride,
An inorganic aqueous solution containing at least one selected from chromates and dichromates and at least one selected from oxides, hydroxides and carbonates of divalent or trivalent metals (a ) And one selected from resin emulsions of epoxy resin, styrene resin, phenol resin, melamine resin, polyester resin, vinyl acetate resin, veova resin, acrylic resin, and silicone resin. Or an organic resin emulsion (b1) comprising two or more kinds and having a resin particle diameter of less than 0.2 μm, an epoxy resin, a styrene resin, a phenol resin, a melamine resin, a polyester resin, a vinyl acetate resin, One or more resin emulsions selected from veova-based resin, acrylic-based resin, and silicone-based resin emulsion, and having a resin particle diameter of 0.3 to 2 An organic resin emulsion (b2) is 5 [mu] m, boric acid and / or boric acid salt, as a main component and an organic reducing agent, and CrO ₃ inorganic component in terms of weight (a) an organic resin emulsion with respect to 100 parts by weight of (b
1) and organic resin emulsion (b2) in a total resin content of 5 to 100 parts by weight, boric acid and / or borate in a total content of 5 to 100 parts by weight, and an organic reducing agent in an amount of 5 to 100 parts by weight. Characterized by having an insulating film having a film thickness of 0.2 to 2.0 μm formed by applying and baking a treatment liquid adjusted to 10 to 80 parts by weight, characterized by having excellent sticking resistance and corrosion resistance. steel sheet.

[3] In the magnetic steel sheet according to the above [1] or [2], the organic resin emulsion (b2) has a resin particle diameter of 0.
An electrical steel sheet excellent in sticking resistance and corrosion resistance, characterized in that the thickness is 6 to 1.5 μm. [4] In the magnetic steel sheet according to [1] or [2], the resin particle diameter of the organic resin emulsion (b2) is 0.6 to 1.0 μm.
An electrical steel sheet excellent in sticking resistance and corrosion resistance, characterized by being:

[5] The magnetic steel sheet according to any one of [1] to [4], wherein the organic resin emulsion (b1) has a resin particle diameter of 0.01 to 0.15 μm. And electrical steel sheet with excellent corrosion resistance. [6] In the magnetic steel sheet according to any one of the above [1] to [5], the compounding ratio of the resin solids of the organic resin emulsion (b1) and the organic resin emulsion (b2) is the weight ratio of the organic resin emulsion (b1) / Organic resin emulsion (b2) = 5
An electromagnetic steel sheet excellent in sticking resistance and corrosion resistance, which is 0/50 to 99/1.

[0016]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The details of the present invention will be described below together with the reasons for limiting the same. In the present invention, the steel sheet serving as the substrate on which the insulating film is formed is an electromagnetic steel sheet for an iron core used for electric equipment such as a motor and a transformer. As such electrical steel sheets, non-oriented electrical steel sheets and grain-oriented electrical steel sheets are generally used, but other than these, mild steel sheets, stainless steel sheets, other special steel sheets, etc. may be used, and the steel sheets serving as substrates are not particularly limited. Not done. The effect of the present invention can be obtained when any of these steel plates is used as a substrate.

The electromagnetic steel sheet to be used as the substrate may be one in which one or more kinds of surface treatments such as a zinc-based plating or other metal plating film and a chemical conversion coating film have been previously applied to the surface thereof. The surface of the steel sheet refers to the surface of the uppermost film when these surface treatment films are provided.

The insulating film formed on the surface of the magnetic steel sheet according to the present invention is formed of at least one selected from chromic anhydride, chromate and dichromate, and a divalent or trivalent metal oxide. An inorganic aqueous solution (a) containing at least one member selected from the group consisting of, hydroxide and carbonate, has a resin particle size of 0.1.
One or two specific resin emulsions that are less than 2 μm
An organic resin emulsion (b1) composed of one or more of a specific resin emulsion having a resin particle diameter of 0.3 to 2.5 μm, and an organic resin emulsion (b2) composed of one or more specific resin emulsions having a resin particle diameter of 0.3 to 2.5 μm. This is a film formed by applying and baking a treatment liquid containing a boric acid and / or a borate and an organic reducing agent.

The aqueous inorganic solution (a) in the treatment solution is at least one selected from chromic anhydride, chromate and dichromate, and an oxide of a divalent or trivalent metal, It is an inorganic aqueous solution containing at least one selected from a substance and a carbonate. As the chromate and dichromate, salts of sodium, potassium, magnesium, calcium, manganese, molybdenum, zinc, aluminum and the like can be used.

The divalent or trivalent metal oxide dissolved in the aqueous solution includes, for example, MgO, CaO, Zn
O, etc., and hydroxides such as Mg (OH) ₂ , Ca (O
H) ₂ , Zn (OH) _2, etc .;
O ₃ , CaCO ₃ , ZnCO _{3 and the} like. These are at least one of chromic anhydride, chromate and dichromate.
The seed is dissolved in the aqueous solution used as the main ingredient to make an inorganic aqueous solution. An inorganic-organic insulating film containing a chromium compound can be formed by these inorganic components.

An organic resin emulsion (b1) and an organic resin emulsion (b2) having different resin particle diameters are blended in the treatment liquid containing the inorganic component. The organic resin emulsion (b1) is a resin emulsion of epoxy resin, styrene resin, phenol resin, melamine resin, polyester resin, vinyl acetate resin, veoba resin, acrylic resin, and silicone resin. A resin emulsion comprising at least one member selected from the group consisting of two or more and having a resin particle diameter of less than 0.2 μm; and the organic resin emulsion (b2) is an epoxy resin, a styrene resin, or a phenol resin. , Melamine resin, polyester resin, vinyl acetate resin, veoba resin,
The resin emulsion is made of one or more resin emulsions selected from acrylic resin and silicone resin, and has a resin particle diameter of 0.3 to 2.5 μm. The present invention is greatly characterized in that two kinds of organic resin emulsions having specific particle diameters having different sizes are added in combination.

When the above-mentioned organic resin emulsion (b1) is used alone as the resin emulsion, the physical effect due to the unevenness of the organic resin itself in the insulating film cannot be obtained during the strain relief annealing after lamination, and the strain relief annealing is not performed. At times, stress concentrates only on the protrusions due to the roughness of the original plate itself, and the stress concentration and the heat generated during annealing destroy the insulating film and cause sticking. On the other hand, when the organic resin emulsion (b2) alone is used as the resin emulsion, especially when the thickness of the insulating film is 0.5 to 0.6 μm or less, the resin particles are less likely to be taken into the film, and The effect of improving the anti-sticking property expected from the resin emulsion (b2) is remarkably reduced, and even if resin particles of the organic resin emulsion (b2) are incorporated into the film, they are easily lost, so that the film defect portion is lost. Occurs, and as a result, the corrosion resistance and the insulation are reduced.

On the other hand, the organic resin emulsion (b)
When 1) and the organic resin emulsion (b2) are added in combination, an insulating film excellent in both sticking resistance and corrosion resistance can be obtained. The reason why excellent properties can be obtained by adding two kinds of organic resin emulsions having specific particle diameters different in size in this manner is not necessarily clear, but by using together with the organic resin emulsion (b1), the organic resin emulsion can be obtained. This is presumably because the emulsion (b2) was easily taken into the film.

The organic resin emulsion (b1) and the organic resin emulsion (b2) are epoxy resin, styrene resin, phenol resin, melamine resin, polyester resin, vinyl acetate resin, veova resin, and acrylic resin. And one or two or more selected from respective resin emulsions of silicone resin. In other organic resin emulsions, the stability in the chromic acid-based inorganic aqueous solution is poor, so it deteriorates shortly after being mixed in the aqueous solution, causing gel-like bumps and gelling of the entire processing solution,
It is not preferable because of practical problems.

When the resin particle diameter of the organic resin emulsion (b1) is 0.2 μm or more, the effect of incorporating the resin particles of the organic resin emulsion (b2) into the film when forming the thin insulating film as described above is obtained. Sufficient sticking resistance and corrosion resistance are not obtained. The more preferable resin particle diameter of the organic resin emulsion (b1) is 0.01 to 0.15 [mu] m, whereby particularly excellent sticking resistance can be obtained.

When the resin particle size of the organic resin emulsion (b2) is less than 0.3 μm, the sticking resistance is poor, while when it is 2.5 μm or more, sufficient corrosion resistance cannot be obtained and the sticking resistance tends to be poor. is there. Also,
When particularly excellent corrosion resistance and sticking resistance are required, the resin particle diameter of the organic resin emulsion (b2) is 0.6 to 1.5 μm, more preferably 0.6 to 1.
Desirably, it is 0 μm.

The amount of the organic resin emulsion (b1) and the organic resin emulsion (b2) in the treatment liquid is
The total amount of the resin solids is preferably 5 to 100 parts by weight based on 100 parts by weight of the inorganic component (a) in terms of rO ₃ . When the total amount of the organic resin emulsion (b1) and the organic resin emulsion (b2) is less than 5 parts by weight, the effect of improving the sticking resistance, corrosion resistance and adhesion by the combined organic resin emulsion can be sufficiently obtained. In addition, since the proportion of the organic resin in the film is reduced, the punching property is also poor. On the other hand, if the amount exceeds 100 parts by weight, the corrosion resistance deteriorates, which is not preferable. Also,
A more preferred range for this amount is 20 to 50 parts by weight.

The compounding ratio of the resin solid content of the organic resin emulsion (b1) / the organic resin emulsion (b2) is as follows:
In particular, the weight ratio is preferably 50/50 to 99/1 from the viewpoints of sticking resistance and corrosion resistance. This compounding ratio is less than 50/50 (organic resin emulsion (b2)
When the ratio exceeds 50%), the corrosion resistance and sticking resistance tend to be inferior. On the other hand, when the ratio exceeds 99/1 (the ratio of the organic resin emulsion (b2) is less than 1%), the sticking resistance tends to deteriorate. It is not preferable because there is. From such a viewpoint, a more preferable range of the compounding ratio is 60/4.
0 to 97/3, more preferably 70/30 to 90
/ 10.

Further, in order to reduce hexavalent Cr ions contained in the processing solution to insolubilize the film, it is preferable to add an organic reducing agent to the processing solution. Usually, polyhydric alcohols such as polyethylene glycol, ethylene glycol, and sucrose are used as the organic reducing agent. The amount of the organic reducing agent is 100 parts of the inorganic component (a) in terms of CrO _3.
It is preferably 10 to 80 parts by weight based on parts by weight. If the compounding amount of the organic reducing agent is less than 10 parts by weight, unreduced hexavalent Cr ions remain, so that the water resistance of the film is poor. On the other hand, if it exceeds 80 parts by weight, the reduction reaction proceeds in the processing solution, Will gel.

Further, it is preferable to add boric acid and / or borate to the treatment solution, because sticking resistance is further improved. The total amount of the boric acid and / or borate is
The content is preferably 5 to 100 parts by weight based on 100 parts by weight of the inorganic component (a) in terms of CrO ₃ . Boric acid and / or
If the total amount of the borate is less than 5 parts by weight, the effect of improving the sticking resistance cannot be sufficiently obtained.
Exceeding the weight part is not preferable because the corrosion resistance is deteriorated.

Further, in the treatment liquid, in addition to the above-mentioned main components, Mg, for the purpose of improving the corrosion resistance and heat resistance of the film, etc.
One or more kinds of Ca, Al or Zn phosphates, and one or more kinds of oxides such as silica can be blended, and the total blending amount of these additional components is CrO ₃ equivalent. If the amount is 20 parts by weight or less based on 100 parts by weight of the inorganic component (a), the basic effects of the present invention are not affected at all.

The insulating film of the magnetic steel sheet of the present invention is formed by applying the above-mentioned treating solution to the surface of the steel sheet and baking it. The thickness of the insulating film is 0.2 μm to 2.0 μm.
The effect of the present invention is particularly effective when the thickness of the insulating film is 0.6 to 0.5.
There is an advantage that even a thin film of μm or less can be obtained without any problem. In the present invention, the thickness of the insulating film refers to the average thickness from the surface of the electromagnetic steel sheet to the outermost layer of the film, but if the film has extreme irregularities, the protrusions of the outermost layer of the film from the surface of the electromagnetic steel sheet And the average of the thickness from the surface of the electromagnetic steel sheet to the concave portion of the outermost layer of the coating.

If the thickness of the insulating film is less than 0.2 μm, the insulation, sticking resistance and corrosion resistance are poor, while if it exceeds 2.0 μm, the space factor and weldability are poor. A particularly preferred film thickness is 0.3 to 1.0 μm. In addition, as a method for forming an insulating film, a method is usually employed in which the above-mentioned treatment liquid is applied to the surface of an electromagnetic steel sheet using a roll coater or the like and then baked in a hot-air drying furnace or an induction heater.

[0034]

EXAMPLES Processing solutions (No. 1 to No. 41) for forming an insulating film shown in Tables 1 to 6 were prepared. These treatment liquids were prepared by adding organic resin emulsions shown in Tables 1 to 6 to an inorganic aqueous solution in which MgO was dissolved in an aqueous solution of chromic anhydride (furthermore, boric acid was included except for No. 27). . These treatment liquids were applied to the surface of an electromagnetic steel sheet having a sheet thickness of 0.5 mm by a roll coater so as to have a predetermined film thickness, and were baked at an ultimate sheet temperature of 280 ° C. to form an insulating film. The following tests were performed on the magnetic steel sheets thus obtained in order to evaluate sticking resistance, corrosion resistance, film adhesion, odor resistance, and punchability. Tables 7 to 9 show the results.

(A) Sticking resistance A steel sheet was punched out to a diameter of 48 mm, 11 sheets were laminated, and annealed (800 ° C. × 2 hours in a N ₂ gas atmosphere) while being tightened at a tightening pressure of 40 kgf / cm ² . . After annealing, the fastening was released, the number of sticks between the plates was checked to determine the sticking position, and the sticking resistance was evaluated based on the number of sticking positions. The evaluation criteria are as follows. ◎: 0 stick occurrences ○ +: 1 to 2 stick occurrences ○: 3 to 4 stick occurrences Δ: 5 to 7 stick occurrences X: 8 or more stick occurrences

(B) Corrosion Resistance The steel sheet was sheared to a size of 70 mm × 150 mm, the back surface and the edge of the test material were sealed, and a salt spray test was performed for 15 hours. The corrosion resistance was determined by the area ratio of red rust after the test. evaluated. The evaluation criteria are as follows. ：: Red rust generation area rate 20% or less ○: Red rust generation area rate 20% or more, 40% or less △: Red rust generation area rate 40% or more, 60% or less ×: Red rust generation area rate 60% or more

(C) Film adhesion (1) No strain relief annealing After subjecting the test material to a bending process of 10 mmφ, a tape peeling test was performed on the bent portion, and the presence or absence of a peeling film on the tape was visually observed. The film adhesion was evaluated by the judgment. (2) With strain relief annealing After subjecting the test material subjected to the strain relief annealing (750 ° C. x 2 hours in an N ₂ gas atmosphere) to a bending process of 10 mmφ, a tape peeling test was performed on the bent portion. The film adhesion was evaluated by visually determining the presence or absence of a release film on the tape. The evaluation criteria for these tests are as follows.

(D) Odor resistance The test materials were punched, laminated, and the end face of the laminate was subjected to TIG.
Welding, the degree of odor (welding gas) generated at that time is 1
The evaluation was performed by 0 evaluators. The evaluation criteria are as follows. ◎: 0 people who felt an unpleasant odor ○: 1 to 3 people who felt an unpleasant odor △: 4 to 5 people who felt an unpleasant odor ×: 6 or more people who felt an unpleasant odor

(E) Punching performance A continuous punching test was carried out using a square die of die material SKD-1 and a light oil-based punching oil with a clearance of 6%, and punching until the burr height reached 50 μm. The number was examined.

[0040]

[Table 1]

[0041]

[Table 2]

[0042]

[Table 3]

[0043]

[Table 4]

[0044]

[Table 5]

[0045]

[Table 6]

[0046]

[Table 7]

[0047]

[Table 8]

[0048]

[Table 9]

[0049]

According to the magnetic steel sheet of the present invention described above,
Both corrosion resistance and sticking resistance are excellent, and
The properties such as film adhesion, odor resistance, and punching property are also good. In addition, even when a thin insulating film having a thickness of 0.6 to 0.5 μm or less is formed, excellent sticking resistance and corrosion resistance can be obtained.

Claims (6)

[Claims] At least one selected from chromic anhydride, chromate and dichromate, and oxides, hydroxides and carbonates of divalent or trivalent metals on the surface of an electrical steel sheet. And an inorganic aqueous solution (a) containing at least one selected from the group consisting of an epoxy resin, a styrene resin, a phenol resin, a melamine resin, a polyester resin, a vinyl acetate resin, a veoba resin, and an acrylic resin. An organic resin emulsion (b1) composed of one or more selected from silicone resin resin emulsions and having a resin particle diameter of less than 0.2 μm, an epoxy resin,
Styrene resin, phenol resin, melamine resin,
Polyester resin, vinyl acetate resin, veova resin, acrylic resin, silicon resin, and one or more resin emulsions selected from each resin emulsion. A coating solution having a thickness of 0.2 to 2.0 μm formed by applying and baking a treatment liquid containing a certain organic resin emulsion (b2) as a main component. Excellent electrical steel sheet. 2. An oxide, hydroxide and carbonate of at least one selected from chromic anhydride, chromate and dichromate on the surface of an electrical steel sheet. And an inorganic aqueous solution (a) containing at least one selected from the group consisting of an epoxy resin, a styrene resin, a phenol resin, a melamine resin, a polyester resin, a vinyl acetate resin, a veoba resin, and an acrylic resin. An organic resin emulsion (b1) composed of one or more selected from silicone resin resin emulsions and having a resin particle diameter of less than 0.2 μm, an epoxy resin,
Styrene resin, phenol resin, melamine resin,
Polyester resin, vinyl acetate resin, veova resin, acrylic resin, silicon resin, and one or more resin emulsions selected from each resin emulsion. Inorganic component (a) containing a certain organic resin emulsion (b2), boric acid and / or borate, and an organic reducing agent as main components and in terms of CrO _3.
The total amount of the organic resin emulsion (b1) and the organic resin emulsion (b2) in terms of resin solid content is 5 to 100 parts by weight, and the total amount of boric acid and / or borate is 5 to 100 parts by weight based on 100 parts by weight. Parts, an insulating film having a film thickness of 0.2 to 2.0 μm formed by applying and baking a treatment liquid in which the amount of the organic reducing agent is adjusted to 10 to 80 parts by weight. Electrical steel sheet with excellent sticking properties and corrosion resistance. 3. The electrical steel sheet according to claim 1, wherein the organic resin emulsion (b2) has a resin particle diameter of 0.6 to 1.5 μm. 4. The magnetic steel sheet according to claim 1, wherein the organic resin emulsion (b2) has a resin particle diameter of 0.6 to 1.0 μm. 5. The sticking resistance and corrosion resistance according to claim 1, wherein the organic resin emulsion (b1) has a resin particle diameter of 0.01 to 0.15 μm. Electrical steel sheet. 6. The compounding ratio of the resin solids of the organic resin emulsion (b1) and the organic resin emulsion (b2) is 50 / 50-99 / organic resin emulsion (b1) / organic resin emulsion (b2) in weight ratio. The electromagnetic steel sheet having excellent sticking resistance and corrosion resistance according to claim 1, 2, or 3.