[0001]The present invention relates to an electromagnetic steel sheet and the electromagnetic steel sheet for a coating solution.
BACKGROUND
[0002]High efficiency and miniaturization of electrical equipment, for the prevention of global warming, also, from the point of view of global energy conservation, is a demand for more and more strongly in recent years. To efficient and compact electrical appliances, it is necessary to various measures, even in the electromagnetic steel sheet used as a motor iron core or a small transformer iron core, such as improvement of improved and workability of the magnetic characteristics It has been demanded.
[0003]
　Generally, the surface of these magnetic steel sheet, insulation coating is applied. Such insulation coating, in addition to the insulation, corrosion resistance, weldability, adhesiveness, there is a need for coating properties such as heat resistance. To achieve high efficiency and miniaturization of electric devices, it is important to suppress the heat generation of the motor (Joule heat), as a measure therefor, and increasing the efficiency of the iron core and windings, the heat radiating plate, etc. the installed such as to enhance the heat extraction of measures it has been made.
[0004]
　Even if performance and efficiency of the electrical steel sheet itself, by processing the electrical steel sheet into a predetermined shape in fabricating motors and transformers, working strain is introduced to the electromagnetic steel sheets. It introduced working strain from degrading the magnetic properties, after processing, by performing a so-called stress relief annealing at consumers, it is more possible to further the efficiency of the electronic device.
[0005]
　On the other hand, the insulating film is coated on the surface of the electrical steel sheet is roughly divided into the following three types.
　　(1) heat resistance is emphasized, 750 ° C. for stress relief annealing is inorganically coating
　　aimed at both weldability and (2) punching resistance, stress relief annealing is possible organic inorganic mixture coating film
　　(3) punching properties There is emphasized, the organic coating is impossible is stress relief annealing
[0006]
　Of the three types of the insulating coating, which is generic, capable of stress relief annealing, an insulating film containing an inorganic component of the (1) and (2). Currently, organic inorganic mixture coating film of the above (2), the appearance as compared with an inorganic coating, punching property, the balance of coating properties, such as adhesion excellent remarkably, has become mainstream.
[0007]
　As shown in (2), as a technique relating to an organic-inorganic mixed insulating film of magnetic steel sheets, for example, a technique as disclosed in Patent Documents 1 and 2 below. Patent Document 1 below, a dichromate, vinyl acetate, butadiene - styrene copolymer, a method of forming the insulating coating is disclosed using the processing solution mainly composed of an organic resin emulsion such as an acrylic resin It is. In Patent Document 2 below is obtained by mixing an aqueous chromic acid solution and emulsion-type resin and an organic reducing agent, an aqueous solution such chromic acid, easily soluble aluminum compound, divalent oxides and H of the metal 3 BO 3 comprises, furthermore, Me chromic acid solution 2+ / Al 3+ molar ratio of an ~ 7.0 0, ((Al 3+ ) + (Me 2+ )) / CrO 3 molar ratio of 0.2 ~ 0.5, and, H 3 BO 3 / CrO 3 with a treatment liquid molar ratio of in the range of 0.1 to 1.5, a technique for forming an insulating coating is disclosed.
[0008]
　Meanwhile, in recent years, the increasing awareness of environmental issues, the development of the insulating coating using no chromic acid aqueous solution containing hexavalent chromium has been promoted. Such techniques, Patent Document 3 below example, and phosphate having a specific composition, boric acid and / or colloidal silica, and a specific ratio blended, and the organic resin emulsion of a specific particle size, baking the steel sheet by having the same film properties and insulation coating containing conventional chromium compounds in the treatment solution containing no chromium compound, and the processing method of holding the slip properties after high stress relief annealing, it is described there.
[0009]
　Further, Patent Document 4 below, and phosphoric acid metal salt, and a resin emulsion having a hydroxyl value and particle size in a specific range, by a certain percentage blend, producing a magnetic steel sheet having excellent insulation coating film properties It discloses a technique.
[0010]
　More recently, in patent document 5 below, the electromagnetic steel sheet having a phosphoric acid metal salt, and an organic resin emulsion is an absolute value of the zeta potential is 30mV or more, an insulating film formed from a treatment solution obtained by blending in a specific ratio to technology has been disclosed about.
[0011]
　As the technology related inorganic coating of the above (1), for example, a technique as disclosed in Patent Document 6 and Patent Document 7 below. Patent Document 6 below, a metal phosphate, and silica or silicate filler retains a specific particle size and specific surface area was specific amount relates to an electromagnetic steel sheet which holds a superior insulating coating on an insulating techniques have been disclosed. Further, Patent Document 7 below, Zr compounds, B compounds, water resistance by containing Si compound at a specific ratio, prevents corrosion degradation, the technology relating to electrical steel sheet with excellent inorganic insulating film to punching properties It has been disclosed.
CITATION
Patent Document
[0012]
Patent Document 1: JP-B 50-15013 Patent Publication
Patent Document 2: JP-A 03-36284 discloses
Patent Document 3: JP-A 06-330338 JP
Patent Document 4: JP 2000-129455 Patent Publication
Patent Document 5: JP 2002-69657 JP
Patent Document 6: WO 2010/146821 Patent
Patent Document 7: JP 2011-246783 JP
Summary of the Invention
Problems that the Invention is to Solve
[0013]
　With high efficiency and miniaturization of the motor and transformers as described above, since the magnetic deterioration due to working strain introduced during processing has become a problem, stress relief annealing is becoming tinged importance. In recent years, when the efficiency of stress relief annealing is required has increased. That is, conventionally, stress relief annealing is carried out at 750 ° C. of about annealing temperature, about 2 hours soaking time was common, in recent years, in order to further improve the productivity, 800 ° C. and 850 ℃ request for a short period of time of raising the annealing temperature to have increased. However, heretofore electromagnetic steel sheet having an organic-inorganic mixture type insulating film was mainstream, not is sufficient heat resistance to contain the organic resin, there is a problem that it is impossible to raise the stress relief annealing temperature.
[0014]
　Further, in the conventional existing inorganic insulating film, or contain chromate, punching properties required for insulation coating of the electrical steel sheet, corrosion resistance, appearance, and heat resistance when the annealing temperature is high or not enough , there is a problem that can not be employed as an insulating film. For the inorganic insulating film, in particular the appearance tends to deteriorate, in order tends to become uneven, there is industrially problem cost increases.
[0015]
　The present invention has been made in view of the above problems, it is an object of the present invention has more excellent heat resistance without containing chromium, corrosion resistance, adhesion and appearance, conventionally also even after carrying out stress relief annealing at high temperatures, it is to provide an electromagnetic steel sheet, and the electromagnetic steel sheet for coating liquid shows excellent insulation properties.
Means for Solving the Problems
[0016]
　The gist of the present invention is as follows.
(1) has the form of secondary particles formed by aggregation of primary particles, in the secondary particles, the average particle size of 0.05μm or more 5μm or less and a specific surface area of 1 ~ 80 m 2 / g and, of the primary particles a plate-shaped inorganic compound fine particles aspect ratio of 50-1000, include a metal phosphate, the content of the plate-shaped inorganic compound fine particles, relative to the phosphoric acid metal salt to 100 parts by mass, 0.1 is 20 parts by mass or less or more parts, having an insulating film not containing chromium on the surface, the electromagnetic steel sheets.
(2) the phosphoric acid metal salt is a salt of Al, Ba, Co, Fe, Mg, Mn, Ni, and, with one or more metal elements and phosphoric acid selected from among Zn, electrical steel sheet according to (1).
(3) the plate-like inorganic compounds, oxides, hydroxides, carbonates, or sulfates, electromagnetic steel sheet according to (1) or (2).
(4) the plate-like inorganic compounds, alumina, gibbsite, silica, talc, kaolin, smectite, or, mica, (1) electrical steel sheet according to any one of - (3).
(5) a non-oriented electrical steel sheet, electrical steel sheet according to any one of (1) to (4).
(6) has the form of secondary particles formed by aggregation of primary particles, wherein the secondary particles, the average particle size of 0.05μm or more 5μm or less and a specific surface area of 1 ~ 80 m 2/ g and a plate-shaped inorganic compound fine particles aspect ratio of the primary particles is 50 to 1000, comprise a solution, of phosphoric acid metal salts, the content of the plate-shaped inorganic compound particles, the metal phosphate relative to 100 parts by weight, and 20 parts by mass or less than 0.1 part by weight, not containing chromium, the coating solution for a magnetic steel.
(7) the phosphoric acid metal salt is a salt of Al, Ba, Co, Fe, Mg, Mn, Ni, and, with one or more metal elements and phosphoric acid selected from among Zn, coating solution described in (6).
(8) the plate-like inorganic compounds, oxides, hydroxides, carbonates, or sulfates, coating solution described in (6) or (7).
(9) the plate-like inorganic compounds, alumina, gibbsite, silica, talc, kaolin, smectite, or, mica, (6) to the coating liquid according to any one of (8).
(10) is a non-oriented electrical steel sheet, (6) to the coating liquid according to any one of (9).
The invention's effect
[0017]
　According to the present invention described above, more excellent heat resistance without containing chromium, corrosion resistance, has adhesiveness and appearance, even after carrying out stress relief annealing at high temperatures than conventional , it is possible to provide an electromagnetic steel sheet exhibiting excellent insulating properties.
DESCRIPTION OF THE INVENTION
[0018]
　The following describes in detail preferred embodiments of the present invention.
[0019]
　Embodiments of the present invention which will be described in detail below, the electromagnetic steel sheet used as an iron core material for electric equipment, which is described electrical steel sheet coating liquid, in particular, the heat resistance was good, and the organic holding the insulating film equal to or more characteristics containing a resin, the electrical steel sheet and the electromagnetic steel sheet for a coating liquid having an insulating film not containing chromium, described in detail.
[0020]

　will be described first electromagnetic steel plates insulating film according to an embodiment of the present invention is formed.
[0021]
　Electromagnetic steel sheet used in the present embodiment (which may be a non-oriented electrical steel sheet) is not particularly limited, in mass%, Si: 0.1% or more, Al: 0.05% containing more, it is preferable to use an electromagnetic steel sheet the balance being Fe and impurities. Si is to increase the electrical resistance in accordance with content increases, is an element for improving the magnetic properties, brittleness is increased simultaneously with the increase in electrical resistance. Therefore, the content of Si is preferably less than 4.0%. Similarly, Al also has an element that the magnetic properties are improved by the inclusion, the rolling resistance decreases with increase of the magnetic properties. Therefore, the content of Al is preferably less than 3.0%.
[0022]
　Further, the electromagnetic steel sheet used in the present embodiment, the above Si, other than Al, instead of a portion of the remainder of Fe, containing a range of 0.01 mass% to 3.0 mass% of Mn it is possible to. Further, in the electromagnetic steel sheet used in the present embodiment, the content of the other S and N, typical element of said C, and preferably less than 100ppm in total, more preferably less than 30 ppm.
[0023]
　Furthermore, electromagnetic steel sheets used in this embodiment may be a directional magnetic steel sheet may be a non-oriented electrical steel sheet. Non-oriented electrical steel sheets are often used for movable portions such as a motor, heat resistance, in addition to the corrosion resistance and the like, but adhesion is required, their insulation coating of the electrical steel sheet according to the present embodiment It has both. Needless to say, the insulating coating of the electrical steel sheet according to the present embodiment, which is often used for non-moving part, such as a transformer, can be applied to grain-oriented electrical steel sheet.
[0024]
　In the present embodiment, annealing in the range ingot (e.g., slab) wound up in a coil shape as hot-rolled sheet by hot rolling, of 800 ° C. ~ 1050 ° C. in the state of the hot rolled sheet optionally having the steel components , then, after cold rolled to a thickness of 0.15 mm ~ 0.5 mm, it is preferable to use not further annealed as an electromagnetic steel sheet. Thickness of the electromagnetic steel sheet used in this embodiment, further preferably 0.25mm or less. Furthermore, when annealing after cold rolling, the annealing temperature is preferably in the range of 750 ℃ ​​~ 1000 ℃.
[0025]
　Furthermore, in the electromagnetic steel sheets used in the present embodiment, since the person surface roughness is relatively small magnetic properties it is improved, which is preferable. Specifically, the rolling direction (L direction), and is preferably the center line average roughness of a direction perpendicular to the rolling direction (C direction) (Ra) is less than 1.0μm, respectively, 0.1 [mu] m or more still more preferably 0.5μm or less. When the center line average roughness Ra is more than 1.0μm is because the tendency of the magnetic characteristics are deteriorated is observed.
[0026]

　on the surface of the above-described magnetic steel sheets (which may be a non-oriented electrical steel sheet), as an insulating film, an insulating film containing no chromium as detailed below is formed. Insulating film formed on the surface of the electrical steel sheet according to the present embodiment includes a metal phosphate, and a inorganic compound fine particles having a specific shape as the main component, and an insulating film containing no chromium. By not containing chromium, the load on the environment is small. The insulating film according to the present embodiment may not contain zirconium (Zr). Zirconium is one of the relatively expensive raw material, by not containing zirconium, it is possible to reduce the cost of the insulating coating. Hereinafter, such an insulating film, will be described in detail.
[0027]
[Phosphoric acid metal salt]
　phosphoric acid metal salt contained in the insulating film according to the present embodiment, the solid content when drying a solution composed mainly of phosphoric acid and metal ions (e.g., aqueous solution, etc.) it become one. The type of the phosphate is not particularly limited, it is possible to use phosphoric acid in various known, for example, orthophosphoric acid, metaphosphoric acid, it is preferable to use a polyphosphoric acid.
[0028]
　As the kind of the metal ion include, but are not particularly limited, it is used Al, Ba, Co, Fe, Mg, Mn, one or more members selected from the group consisting of Ni and Zn it is preferred, in particular, it is more preferred to use at least one of Al and Zn.
[0029]
　Here, in preparing the phosphoric acid metal salt solution, various phosphoric acid (solution, in particular may be an aqueous solution) of such orthophosphoric acid to, oxides of metal ions, carbonates and, hydroxide it is preferable to mix at least one of things.
[0030]
[Tabular inorganic compound particles]
　The insulation in the coating according to the present embodiment, as one of the main components, a plate-shaped inorganic compound fine particles (hereinafter, also referred to as "plate-shaped inorganic compound fine particles.") Is contained.
[0031]
　Plate-like inorganic compound fine particles according to the present embodiment, the form of secondary particles formed by aggregation of primary particles, the secondary particles, the average particle size of from 0.05μm or more 5μm or less. Further, the plate-shaped inorganic compound fine particles according to the present embodiment, the secondary particles, the specific surface area described below, 1 ~ 80 m 2 are within the range of / g. Further, the plate-shaped inorganic compound fine particles according to the present embodiment, in the primary particles, the aspect ratio to be described below, are within the range of 50-1000. In this embodiment, the primary particles are plate-like satisfying the aspect ratio of the above or foliar or has a shape of scale-like, its primary particles aggregate to form secondary particles. In the secondary particles, irregularly overlap each other primary particles, a space is formed in the secondary particles. At least a portion of the space may be a space that opens to the surface of the secondary particles, may be a closed space. The secondary particles such having a complex form, the above average particle diameter, filled with the specific surface area and primary particle is defined by satisfying the range of the aspect ratio.
[0032]
　As a component of a plate-like inorganic compound fine particles as described above, for example, oxides, hydroxides, carbonates, and at least one is preferably a sulfate, chloride, nitrate, nitride, or bromides, etc. unfavorable. Of such inorganic compounds, as the oxide, specifically, alumina, there may be mentioned talc, kaolin, silica and the like, Examples of the hydroxide, and the like can be illustrated gibbsite, as the mineral, smectite , and the like mica.
[0033]
　The average particle diameter of the secondary particles of the plate-shaped inorganic compound particles, is less than 0.05 .mu.m, since the coating property is deteriorated, which is not preferable. On the other hand, the average particle diameter of the secondary particles of the plate-shaped inorganic compound fine particles, if it exceeds 5 [mu] m, since the space factor is lowered, unfavorably.
[0034]
　The average particle diameter of the plate-like inorganic compound fine particles as described above, it is possible to measure by known methods, in the secondary particles of the plate-shaped inorganic compound fine particles according to the present embodiment, a laser diffraction- It means a particle diameter at an integrated value of 50% in the particle size distribution determined by the scattering method.
[0035]
　The specific surface area of the, intended to be measured by the gas adsorption method, conforming to JIS-K6217. The specific surface area of the secondary particles of the plate-shaped inorganic compound fine particles 1.0 m 2 of less than / g, the treatment liquid the secondary particles (coating solution) in the time consuming to mix becomes easily sediment and suspended a specific surface area of 80.0M 2 in / g greater tend to the secondary particles in the treatment liquid (coating liquid) is agglomerated to coating defects during drying baking. Therefore, in the present embodiment, the average specific surface area of 1.0 ~ 80.0M 2 is in the range of / g.
[0036]
　Further, the above-mentioned aspect ratio means the ratio between the diameter and the thickness of the primary particles of the plate-shaped inorganic compound fine particles (diameter / thickness). Further, the diameter of the primary particles of the plate-shaped inorganic compound particles, when projecting the primary particles from every direction, is that the diameter of the primary particle surfaces (projection plane) having the largest projected area. Thickness for defining the aspect ratio, the thickness of the primary particles in a direction perpendicular to the projection plane to provide a diameter. Also even when any regards the outer shape of the target plate-like inorganic compound fine particles and circular, the ratio between the diameter and the thickness of such a circle (more specifically, (a value given by the diameter / thickness)), and the aspect ratio to.
[0037]
　Here, the diameter and thickness used to define the aspect ratio can be measured by a known measurement method. In this embodiment, the aspect ratio was observed with a scanning electron microscope (SEM), JIS Z8827-1 "particle size analysis - image analysis method - Part 1: Static image analysis method" by the analysis method specified in Ask. Unless otherwise noted, in the present specification, the aspect ratio, using the JEOL Ltd. JSM-7000F, by observing the SEM images taken at approximately 5000-fold, which was determined. The aspect ratio is the average value of the aspect ratio of at least 10 particles. The aspect ratio of primary particles, through observation of the SEM image of the secondary particles is measured. Although the primary particles are aggregated to form secondary particles, the expansion and angle adjustment of the secondary particle image is accurately observable primary particles constituting the secondary particles, calculated aspect ratio of primary particles it can. The aspect ratio of primary particles measured by this method is considered to represent the aspect ratio of the primary particles of the actual insulating in the coating.
[0038]
　Incidentally, when the aspect ratio of the is less than 50, since the solution poor appearance becomes unstable easily occur, which is not preferable. Meanwhile, the aspect ratio described above in the case of more than 1000 forming irregularities on the insulating coating tends to occur that the adhesion may be degraded, which is not preferable. Such aspect ratio is preferably in the range of 100-500.
[0039]
　Previously, in the secondary particles of the plate-shaped inorganic compound fine particles, average particle size, specific surface area, and it has been described respective numerical limitation reasons of the three items of the aspect ratio of the primary particles, a plate according to an embodiment of the present invention Jo inorganic compound fine particles are those satisfying all of these items simultaneously. While not wishing to be bound by any particular theory, it is believed the following. Secondary particles in which primary particles of the aspect ratio are aggregated to form a complex form which satisfies the above average particle diameter and specific surface area. And by proper space is formed by the complex form the insulating property of the insulating film, the heat resistance is improved. The space is phosphoric acid metal salt is likely to penetrate, corrosion resistance to further achieve an anchor effect improves the adhesion, thus contributing to the improvement of the appearance.
[0040]
　In the insulating film according to the present embodiment, the content of the plate-like fine particles of the inorganic compound per 100 parts by mass of the metal phosphate, and 20 parts by mass or less than 0.1 part by weight. When the content of the plate-like inorganic compound fine particles is less than 0.1 part by weight is not exerted to the effect sufficiently as was contained such plate-like inorganic compounds, is undesirable. On the other hand, if the content of the plate-shaped inorganic compound fine particles is more than 20 parts by weight, there is a possibility that adhesion after stress relief annealing the film formability is degraded to deteriorate, unfavorably. The content of the plate-like fine particles of the inorganic compound, preferably, with respect to 100 parts by weight of metal phosphate, 10 parts by mass or less than 0.5 part by weight.
[0041]
　The electromagnetic steel sheet according to the present embodiment, as described above, the phosphoric acid metal salt having a specific composition, a specific inorganic compound fine particles, that is formed on the surface of the insulating film is contained in a specific ratio, electrical steel it is possible to improve the heat resistance of the insulating coating. The reason why the heat resistance is improved by forming an insulating film having a component as described above, it is the details of which are not known, the specific metal phosphate around the inorganic compound fine particles are compound, heat resistance There is assumed that improved. Further, since the secondary particles of the inorganic compound particles have a complex shape, by acting as an anchor for metal phosphate, corrosion resistance, improved adhesion, resulting in turn excellent appearance. On the surface of the electrical steel sheet having, by forming such an insulating film can be carried out stress relief annealing at high temperatures than conventional, i.e. heat resistance. Furthermore, it is possible to realize the insulation properties superior even after stress relief annealing.
[0042]
[Adhesion amount of the insulating coating]
　An electromagnetic steel sheet according to the present embodiment, the adhesion amount of above-described insulating film (inorganic insulating film) is not particularly limited but, for example, 0.5 g / m 2 or more 2. 5 g / m 2 is preferably in the following range. Adhesion amount of the insulating coating is 0.5 g / m 2 when it is less than consists interlayer resistance, etc. is liable to deteriorate, there is a possibility that the insulating properties of the holding becomes difficult. On the other hand, the adhesion amount of the insulating coating is 2.5 g / m 2 in the case of more than is likely to tend to adhesion is degraded becomes remarkable. Adhesion amount of the insulating coating is more preferably, 0.5 g / m 2 or more 1.0 g / m 2 or less.
[0043]
　Here, the solid content in the treatment liquid (coating liquid) in used to form the insulating coating is substantially equal to the coating weight of the insulation coating as described above, the treatment liquid (coating liquid) used for forming the insulating film in ratio of the phosphoric acid metal salt and plate-like inorganic compound fine particles in is substantially equal to the ratio of the content of the phosphoric acid metal salt and plate-like inorganic compound fine particles in the insulating film as described above. In the case of post-measure the deposition amount of the insulating coating, it is possible to use various known measuring methods, for example, a method of measuring the difference in weight prior to and subsequent aqueous sodium hydroxide dipping, calibration curve Law fluorescent X-ray method or the like may be suitably utilized with. Similarly, in the case of ex-post measuring the content of the plate-like fine particles of the inorganic compound, it is possible to use various known measuring methods, for example, suitably a fluorescent X-ray method using a calibration curve method it may be utilized.
[0044]
[Formation method of the insulating film]
　In the present embodiment, the processing liquid containing the components described above (coating solution) was adjusted, even such a treatment liquid (coating liquid) an electromagnetic steel plate (non-oriented electrical steel sheet be to coating and drying on the surface of the good), it is possible to form an insulating coating as described above. As an embodiment of the present invention, the above components may be provided a coating liquid for an electromagnetic steel sheet containing at a content above. This coating liquid, the above-mentioned insulating film can be obtained.
[0045]
　Treatment liquid (coating liquid) is the plate-shaped inorganic compound fine particles in advance, the various solutions, the dispersions obtained by addition of dispersing the tabular inorganic compound fine particles, by adding phosphoric acid metal salt aqueous solution described above, the preparation can do.
　Plate-like inorganic compound fine particles is previously in various solvents, it is possible to use those obtained by adding dispersing plate inorganic compound fine particles. As a dispersion solvent, in addition to pure water, dioxane, an organic solvent such as ethanol may be used as appropriate.
　Here, the solid content in the treatment liquid (coating liquid) (plate-like inorganic compounds, and phosphoric acid metal salt), since substantially equal to the coating weight of the insulating coating, metal phosphate in the treatment liquid (coating liquid) ratio of the salt and the plate-shaped inorganic compound fine particles, so as to be substantially equal to the ratio of the content of the phosphoric acid metal salt and plate-like inorganic compound fine particles in the insulating film is adjusted.
[0046]
　In the case of applying the treatment liquid (coating liquid) on the electrical steel sheet surface, the coating method is not particularly limited, it is possible to suitably use a known coating method. When applying the treatment liquid (coating liquid), for example, may be a roll coater method, spray method, it may be used coating method such as dipping method.
[0047]
　As for the heating method at the time of heating and drying the applied treatment liquid (coating liquid), it is not particularly limited, it is possible to suitably use a known heating methods. As the heating method, for example, a method may be used by conventional radiant furnace, may be used heating method using electricity, such as induction heating system, but in terms of control accuracy of heating rate, an induction heating method it is more preferable to use. Using these heating system, the processing liquid a temperature above the boiling point of the solvent (coating solution) by holding a predetermined time, it is possible to form the insulating coating.
[0048]
　Incidentally, in the above treatment liquid (coating liquid), further, it may contain an additive such as a surfactant. Such surfactants, for example, it is preferable to use a nonionic surfactant. Further, in the above treatment liquid (coating liquid), it may be contained and other brighteners.
[0049]
　Although the insulation coating in the electromagnetic steel sheet according to the present embodiment has been described in detail.
[0050]
　As described above, the electromagnetic steel sheet according to the present embodiment, phosphoric acid metal salt having a specific composition and a specific inorganic compound fine particles, that is formed on the surface of the formed insulating film in a specific ratio, the electrical steel sheet heat resistance of the insulating coating, corrosion resistance, by improving the adhesiveness, it is possible to obtain the insulating properties and good holding appearance electromagnetic steel sheet after stress relief annealing at high temperatures than conventional. In an embodiment of the present invention, it is possible to form the insulating coating of the electromagnetic steel sheet, can also provide for electrical steel sheet coating liquid.
Example
[0051]
　Subsequently, while indicating embodiments, the electromagnetic steel sheet according to the present invention will be specifically described. Incidentally, what is relevant to the present invention Examples of the examples that follow, are merely one example of an electromagnetic steel sheet according to the present invention, an electromagnetic steel sheet according to the present invention is not limited to the following examples.
[0052]
　Prepare the following various plate-like inorganic fine compounds shown in Table 1, these plate-shaped inorganic compound fine particles are contained in a phosphoric acid metal salt solution shown in Table 2 at a content shown in Table 1, as appropriate pure as density adjustment water was added to stirred, and the treatment liquid for insulation film formed with (coating liquid).
[0053]
　By mass%, Si: 3.1%, Al : 0.6%, Mn: containing 0.1% the balance being Fe and impurities, the thickness is 0.30 mm, L direction and C direction on the surface of the non-oriented electrical steel sheet surface roughness of is 0.28μm respectively Ra (centerline average roughness), the above treatment liquid (coating liquid) the coating amount is 1.2 g / m 2 so that the the coating with a roll coater, in a heating furnace at 500 ° C. and baked for 60 seconds so as sheet temperature becomes 350 ° C., to form an insulating film.
[0054]
　Incidentally, the plate-shaped inorganic compound fine particles shown in Table 1 below, in advance, the various solvents were used those obtained by adding dispersing plate inorganic compound fine particles. As the solvent, in addition to pure water, using dioxane, the organic solvent such as ethanol as appropriate. Thereafter, water and to a solvent 100 parts by weight of the following plate-like inorganic compound fine particles to those obtained by 10 parts by dispersing a metal phosphate aqueous solution was added, in the solid in the coating amount, relative to 100 parts by weight of phosphoric acid metal salts , inorganic compound treatment solution so as to have a predetermined mass in the chart (coating solution) was prepared. In some cases, a dispersant such as a surfactant was also used as appropriate.
[0055]
　Further, in the following Table 2, each metal phosphate, using a commercially available aqueous phosphate solution, the proportion of solids by the addition of pure water was adjusted to 30 wt%, phosphorus of the respective metal elements were mixed so that the ratio in the acid metal salt. Note that the generation of the phosphoric acid metal salt shown in Table 2, as phosphoric acid, using orthophosphoric acid.
[0056]
　Here, the following for each of the indicated inorganic compound in Table 1, the aspect ratio as shown below, has a specific surface area and average particle diameter (D50), using a commercially available for each compound. Incidentally, each compound shown in Table 1, the average particle size (D50) of, and specific surface area, respectively be those in the secondary particles, a catalog value, the aspect ratio, there is in the primary particles, each is a value calculated from the actual measurement value measured by scanning electron microscopy of the compound.
[0057]
　In Table 2 of the treatment liquid (coating liquid) of the following, as the metal source in the metal phosphate, and a commercially available following compounds. In addition, for the chromic acid Mg, using a commercially available.
[0058]
Al:
　　Al (OH) 　　3 Ba: Ba 　　(OH) 2 Co: Coco 3 　　Fe: Fe 3 O 4 Mg: Mg (OH) 2 　　Mn: MnO Ni: Ni 　　(OH) 2 Zn: ZnO 　　Ca CaO K: KOH

[0059]
[Table 1]

[0060]
[Table 2]

[0061]
　An insulating film obtained as described above were evaluated by the following method, the results obtained are shown in Table 3 below.
[0062]

　insulative, based on the inter-layer resistance was measured according to JIS method (JIS
　　C2550), 4: 30 [Omega · cm 2 / sheet or more
　　3: 10 [Omega · cm 2 / sheet or more 30 [Omega · cm 2 less than / sheets
　　2: 3Omu · Cm 2 / or more sheets · Cm 10Omu 2 / sheet less than
　　1: 3Omu · Cm 2 less than / sheet
was evaluated as, was passed a score of 3 or more.
[0063]

　corrosion resistance, carried out according to the salt spray test of JIS method (JIS Z2371), were performed in 10-point evaluation sample after 4 hours aging. The evaluation criteria are as follows, it was passed a score of 6 or more.
[0064]
　　10: rust was not
　　　9: amount rust is very small (less area ratio
　　　0.1%) 8: rust occurred area ratio of = 0.1% excess 0.25% or less
　　　7: occurred area ratio of rust = 0.25% exceeds 0.50% or less
　　　6: rust occurred area ratio of = 0.50% excess of 1% or less
　　　5: rust occurred area ratio of = 1% excess 2.5%
　　　4: rust occurrence the area ratio = 2.5% excess 5%
　　　3: rust occurred area ratio of = 5% excess of 10% or less
　　　2: rust occurred area ratio of = 10% excess of 25% or less
　　　1: occurred area ratio of rust = 25% excess of 50% or less
[0065]

　heat resistance was evaluated by the corrosion resistance after stress relief annealing. For 1 hour heat treatment in a 100% nitrogen atmosphere at 850 ° C., followed by a temperature 50 ° C., after 48 hours passes at constant temperature and humidity bath at a humidity of 90%, it was evaluated corrosion resistance similar to rust area ratio . The evaluation criteria are as follows, it was passed a score of 6 or more.
[0066]
　　10: rust was not
　　　9: amount rust is very small (less area ratio
　　　0.1%) 8: rust occurred area ratio of = 0.1% excess 0.25% or less
　　　7: occurred area ratio of rust = 0.25% exceeds 0.50% or less
　　　6: rust occurred area ratio of = 0.50% excess of 1% or less
　　　5: rust occurred area ratio of = 1% excess 2.5%
　　　4: rust occurrence the area ratio = 2.5% excess 5%
　　　3: rust occurred area ratio of = 5% excess of 10% or less
　　　2: rust occurred area ratio of = 10% excess of 25% or less
　　　1: occurred area ratio of rust = 25% excess of 50% or less
[0067]

　adhesion was evaluated by the sliding test after stress relief annealing. Cylinder in wound filter paper 45C of 20 mm.phi, load 100 gf (1 gf is, 9.8 × 10 -3 is N.) By applying a, when 5 is reciprocated surface of the insulating coating, coating residue adhering to the filter paper the amount of the measurement. Evaluation criteria are as follows, and as acceptable score 3 or higher.
[0068]
　　5: No residue
　　4: negligible residues appear linear.
　　3: clear and residue adheres.
　　2: The residue is the width in a strip.
　　1: residue powdery adheres to the filter paper.
[0069]

　The appearance of the insulating coating, the appearance inspection of the non-oriented electrical steel sheet with the obtained insulating film, and implemented by skilled inspectors,
　　5: shiny, what is uniform smooth
　　4: Gloss those slightly inferior to some but uniformity
　　3: slightly shiny there some smooth but inferior in uniformity
　　2: gloss is small, inferior slightly inferior uniformity in smoothness
　　1: gloss uniformity, smoothness inferior
evaluated as, it was passed a rating of 4 or more.
[0070]
[table 3]

[0071]
　As is apparent from Table 3, the surface of the steel sheet, the form of secondary particles formed by aggregation of primary particles, in the secondary particles, the average particle size is at 0.05μm or 5μm or less, the specific surface area 1 ~ 80 m 2 was / g, and the aspect ratio of 50-1000 plated mineral compound fine particles of the primary particles, and a phosphoric acid metal salt, the content of the plate-shaped inorganic compound fine particles, metal phosphate 100 to parts by weight, 0.1 to 20 parts by weight, the electromagnetic steel sheet of the present invention having an insulating film not containing chromium, insulation resistance as compared with Comparative example, corrosion resistance, adhesion, excellent appearance, and further , the effect of improving the heat resistance to withstand stress relief annealing at a high temperature is remarkable.
[0072]
　Having described in detail preferred embodiments of the present invention, the present invention is not limited to such an example. It would be appreciated by those skilled in the relevant field of technology of the present invention, within the scope of the technical idea described in the claims, it is intended to cover various changes and modifications , also such modifications are intended to fall within the technical scope of the present invention.

WE CLAIM

The form of secondary particles formed by aggregation of primary particles, wherein the secondary particles, the average particle size of 0.05μm or more 5μm or less and a specific surface area of 1 ~ 80 m 2 was / g, and the aspect of the primary particles the ratio and 50 to a 1000 plate inorganic compound fine particles comprise a metal phosphate, the content of the plate-shaped inorganic compound fine particles, relative to the phosphoric acid metal salt to 100 parts by mass, 0.1 parts by weight and not more than 20 parts by mass or less, an insulating film containing no chromium on the surface, the electromagnetic steel sheets.
[Requested item 2]
　The phosphoric acid metal salt is a salt of Al, Ba, Co, Fe, Mg, Mn, Ni, and, with one or more metal elements and phosphoric acid selected from among Zn, claim 1 electromagnetic steel sheet according to.
[Requested item 3]
　The plate-like inorganic compounds, oxides, hydroxides, carbonates, or sulfates, electrical steel sheet according to claim 1 or 2.
[Requested item 4]
　The plate-like inorganic compounds, alumina, gibbsite, silica, talc, kaolin, smectite, or, mica, electrical steel sheet according to any one of claims 1-3.
[Requested item 5]
　It is a non-oriented electrical steel sheet, electrical steel sheet according to any one of claims 1-4.
[Requested item 6]
　 The form of secondary particles formed by aggregation of primary particles, in the secondary particles, the average particle size of 0.05μm or more 5μm or less and a specific surface area of 1 ~ 80 m 2 / g and an aspect ratio of the primary particles is 50 and a 1000 plate inorganic compound fine particles comprise a solution, of phosphoric acid metal salts, the content of the plate-shaped inorganic compound fine particles with respect to the 100 parts by weight of metal phosphate, 0.1 part by mass or more and 20 parts by mass or less, does not contain chromium, the coating liquid for the magnetic steel.
[Requested item 7]
　The phosphoric acid metal salt is a salt of Al, Ba, Co, Fe, Mg, Mn, Ni, and, with one or more metal elements and phosphoric acid selected from among Zn, claim 6 coating solution described in.
[Requested item 8]
　The plate-like inorganic compounds, oxides, hydroxides, carbonates, or sulfates, coating solution according to claim 6 or 7.
[Requested item 9]
　The plate-like inorganic compounds, alumina, gibbsite, silica, talc, kaolin, smectite, or, mica, a coating solution according to any one of claims 6-8.
[Requested item 10]
　Is a non-oriented electrical steel sheet, the coating liquid according to any one of claims 6-9.