JP2012046825A - Heat resistant adhesive insulating film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide: an electromagnetic steel sheet having a surface covered with a heat resistant adhesive insulating film which, after lamination, can be bonded by pressing and heating and can achieve strain relieving annealing; an iron core using the electromagnetic steel sheet; and a process for manufacturing the same.SOLUTION: The electromagnetic steel sheet is covered with a heat resistant adhesive insulating film comprising a resin which softens at room temperature or above and 300°C or below, and a low-melting inorganic component having a softening temperature of 1,000°C or below as measured by a differential thermal analysis method, and formed by mixing the resin and the low melting point inorganic component at a mixing ratio of 20% or more and 500% or less by mass fraction. A strain-relieving-annealable bonded fixed iron core is provided by stacking this electromagnetic steel sheet and conducting press fixation.

Description

  The present invention can be bonded after lamination by pressurization and heating (in the present invention, it refers to a heat treatment at room temperature or higher and 300 ° C. or lower unless otherwise specified), and thereafter annealing treatment such as strain relief annealing (in the present invention Refers to a heat-resistant adhesive coating composition that can maintain the adhesive ability even if it is subjected to a heat treatment of more than 300 ° C. unless otherwise specified, and a surface-coated electrical steel sheet.

  Electrical steel sheets are mainly used as iron cores for motors and transformers. Usually, the surface of an electromagnetic steel sheet is formed with an insulating coating, and after being continuously punched into a predetermined shape, it is integrated by a method such as stacking and welding, or by fitting uneven portions called caulking. It is common to form an iron core.

  The integrated iron core may be used by being incorporated in an electric device as it is, or may be incorporated in an electric device after being annealed at a temperature of about 700 ° C. to 800 ° C. The latter annealing is called strain relief annealing, and it removes or reduces the shear strain introduced into the steel sheet during punching / shearing, thermal strain generated by welding of the end faces, and plastic deformation strain of the caulking portion by annealing. In order to enhance the magnetic characteristics of the iron core, the iron core is used for electric equipment applications that require high electric efficiency.

  In the method of integrating the magnetic steel sheets laminated by welding or caulking, there are problems that the core edge portion is short-circuited and insulation is lowered, and that magnetic properties are deteriorated due to processing strain. As a method for avoiding defects due to welding or caulking, a technique has been proposed in which an insulating coating exhibiting adhesiveness is formed on a magnetic steel sheet in advance by thermocompression bonding, and after stamping or shearing, is laminated and thermocompression bonded.

  For example, a method for producing a surface-coated electrical steel sheet for bonding (Patent Document 1) or foaming, characterized in that a mixed liquid mainly composed of an acrylic modified epoxy resin emulsion containing a latent curing agent is applied and incompletely baked. A magnetic steel sheet with an insulating coating coated with an adhesive resin containing an agent (Patent Document 2), and also the techniques of Patent Document 3 and Patent Document 4 have been proposed. These so-called adhesive coating technologies can alleviate the problems caused by caulking and welding, but since the surface of the steel sheet is coated only with organic matter, many of them decompose at temperatures of 300 ° C or higher, and strain relief annealing is performed. If applied, the adhesive strength cannot be maintained. For this reason, it is possible to use a magnetic steel sheet with an adhesive coating for an iron core that does not undergo strain relief annealing, but it cannot be used for an iron core that undergoes strain relief to reduce iron loss. was there.

  On the other hand, it is also possible to use a method in which an electrical steel sheet processed by punching or the like into a predetermined shape is subjected to strain relief annealing and then fixed by an adhesive, but it is necessary to apply an adhesive to each small punched piece. The nature is bad.

  Patent Documents 5 to 7 disclose so-called inorganic coating films that do not contain a resin component. Since Patent Document 5 does not have a bonding function between steel plates, an integrated iron core cannot be obtained unless a fixing method other than bonding such as caulking or welding is performed. Patent Documents 6 and 7 have the problem that the film is hard because it is an inorganic film composed only of a low-melting glass component, and the punching die is adversely affected, and there is also a large amount of dust generation.

Japanese Patent No. 2613725 JP 2002-260910 A Japanese Patent Publication No.55-9815 Japanese Patent Laid-Open No. 2-208044 Japanese Examined Patent Publication No. 42-24519 JP 58-128715 A Japanese Patent Publication No. 47-47499

  The present invention improves the heat resistance of the adhesive insulating coating of the electrical steel sheet with the adhesive insulating coating, and the heat-resistant adhesive insulating coating that maintains the adhesive state and the insulating property even after strain relief is applied, and the same The present invention provides an electromagnetic steel sheet with a heat-resistant adhesive coating, an iron core using the electromagnetic steel sheet, and a method for producing the same.

In order to solve the above problems, the present invention uses the following means.
(1) A heat resistant adhesive insulating coating comprising a resin having a softening point temperature of room temperature to 300 ° C. and a low melting point inorganic component having a softening point temperature of 1000 ° C. or less.
(2) 250 ° C. adhesive strength = 10 kg / cm ² or more and 750 ° C. adhesive strength = 1 kg / cm ² or more.
(3) The heat resistance according to (1), wherein the linear thermal expansion coefficient at 30 to 300 ° C. is 10 × 10 ⁻⁷ (° C. ⁻¹ ) or more and 150 × 10 ⁻⁷ (° C. ⁻¹ ) or less. Adhesive insulating coating.
(4) The heat-resistant adhesive insulating coating according to (1), wherein the low-melting-point inorganic component is a low-melting-point glass frit, water glass, or a mixture of them with colloidal silica.

(5) The heat-resistant adhesive insulating coating according to (4), wherein the low melting point inorganic component has an average particle size of 20 μm or less.
(7) The heat-resistant adhesive insulating coating according to (4), wherein the low-melting-point inorganic component is SiO ₂ —B ₂ O ₃ —R ₂ O-based low-melting glass (R is an alkali metal).
(8) The heat-resistant adhesive insulating coating according to (4), wherein the water glass is sodium silicate.
(9) The resin is an epoxy resin, an acrylic resin, a phenol resin, a resin in which a mixed liquid mainly composed of an acrylic modified epoxy resin emulsion previously blended with a latent curing agent is baked in an incomplete state, or a siloxane polymer. The heat-resistant adhesive insulating coating according to (1), comprising one or more selected.
(10) A magnetic steel sheet with a heat-resistant adhesive insulating coating, having the coating according to (1) on at least one side of the steel plate.
(11) The electrical steel sheet with a heat resistant adhesive insulating coating according to (10), wherein the thickness of the heat resistant adhesive insulating coating is 0.5 μm or more and 20 μm or less.
(12) An iron core using the electrical steel sheet with a heat-resistant adhesive insulating coating according to (10).
(13) Heat-resistant adhesive insulation in which the magnetic steel sheet according to (10) is laminated and pressure-fixed to produce an electromagnetic steel sheet laminate, which is then annealed at 600 to 900 ° C. to obtain an integrated iron core. A method of manufacturing an iron core using a coated electromagnetic steel sheet.
(14) At least in the stage of pressure fixation, heating and adhesive fixing, fixing by caulking or a jig, or a combination thereof, the electrical steel sheet with a heat-resistant adhesive insulating coating according to (13) The manufacturing method of the iron core used.

  In the present invention, the composition of the insulating coating of the electrical steel sheet is combined to exhibit two types of adhesiveness, and as a specific means, it is measured by a resin that softens at room temperature to 300 ° C. and differential thermal analysis. It is a film containing a low-melting-point inorganic component having a softening point temperature of 1000 ° C. or lower. The resin of the coating serves to soften and integrate the iron core during hot pressing, and the low melting point inorganic component serves to maintain the iron core in an integrated state when the iron core is strain-relieved.

It is a figure which shows the general differential thermal analysis curve of glass. It is a figure which shows a ladder-like siloxane polymer.

  In order to remove the strain from the steel plate, a temperature of about 700 to 800 ° C. is usually required as the annealing temperature. At such an annealing temperature, the organic matter is decomposed and the structure cannot be maintained, so that the adhesion cannot be maintained. The inventors considered that an inorganic compound is suitable for maintaining the structure even at a high temperature of 700 ° C. to 800 ° C. and exhibiting the adhesiveness between the steel plates, and studied various inorganic compounds. As a result, it was found that a group of low-melting-point inorganic components called so-called low-melting-point glass frit and low-melting-point inorganic components such as water glass and colloidal silica exhibit good adhesion between steel plates at around 750 ° C annealing temperature condition. . However, these low-melting-point inorganic components alone cannot achieve the integral holding of the iron core because the adhesive ability is not exhibited in the stage before the completion of annealing. Thus, it has been found that by combining a resin with these, an iron core can be obtained which can be bonded and fixed before the strain relief annealing and can maintain the adhesion fixing ability even after the strain relief annealing.

Hereinafter, the low melting point inorganic component will be described first. The inventors have found that it is the softening point temperature of the low-melting-point inorganic component that dominates the adhesiveness in the strain relief annealing temperature range.
The details of experiments conducted to complete the invention will be described below.

In order to confirm the importance of the above-mentioned softening point temperature, the inventors prepared a sample under the following conditions and investigated its adhesive strength. First, a large number of non-oriented electrical steel sheets having a plate thickness of 0.5 mm and having no insulating coating on the surface were prepared. On the other hand, the low melting point inorganic component is a low melting point glass frit having an average particle size of 5 μm and various softening point temperatures, and the resin is epoxy resin: acrylic resin: phenol resin = 15: 3: 3 (mass%) Both were mixed using the water emulsion liquid of 20 mass% of solid content, and it apply | coated using the roll coater. The mixing ratio of the resin to the glass frit was 100% in terms of solid content, that is, the same mass. The coating amount was 8 g / m ² per side and dried at a plate temperature of 160 ° C. A test piece was cut out from the sample thus prepared. Subsequently, 250 degreeC adhesive strength and 750 degreeC adhesive strength were measured.

  Here, the softening point temperature is the temperature of the fourth inflection point observed after the start of measurement in the differential thermal analysis measurement curve shown in FIG. 1, or JIS-R3103-1 “Glass softening point test method”. (ISO 7884-6: 1987, ASTM C338), whichever is the lower temperature, but if any of these methods are difficult to measure, other softening point temperatures may be substituted.

The 250 ° C adhesive strength is 10 kg in the rolling direction and 3 cm long in the direction perpendicular to the rolling direction. The applied pressure is 10 kg with the short side overlapped by 1 cm and area of 3 cm ^2. / 3 cm ² , heating temperature 250 ° C., heating time 60 seconds, after bonding, the value when it was pulled in the rolling direction at room temperature and peeled was divided by an area of 3 cm ² . In the present invention, the applied pressure and adhesive strength are values obtained by dividing the indicated value (kg) of the spring balance by the area, and expressed as kg / cm ² , which corresponds to 9.8 × 10 ⁴ Pa.

The 750 ° C adhesive strength refers to a sample bonded under the above-mentioned low temperature bonding conditions, further heated in the condition of a heating temperature of 750 ° C and a heating time of 2 hours without being pressurized, and then pulled in the rolling direction at room temperature. The strength when peeled is divided by an area of 3 cm ² . The results are shown in Table 1.

From Table 1, when using a glass frit with a condition number 1 to condition number 8 and a softening point temperature of 1000 ° C. or less, the 250 ° C. bond strength is 10 kg / cm ² or more and the 750 ° C. bond strength is 1 kg / cm ^2. It can be seen that cm ² and both values are good. On the other hand, when a glass frit with a softening point temperature of 1050 ° C in Condition No. 9 is used, the adhesive strength at 250 ° C is 10kg / cm ² , but the adhesive strength at 750 ° C is easily peeled off after annealing. It was so weak that it could not be measured. Based on the above, when using a glass frit with a softening point temperature of 1000 ° C or less, the 250 ° C adhesive strength is 10 kg / cm ² or more and the 750 ° C adhesive strength is 1 kg / cm ² , both of which are good. found.

  Next, the inventors consider the following mechanism as to the reason why the 750 ° C. adhesive strength depends on the softening point temperature of the low melting point inorganic component. The resin softens and melts at the time of pressurizing and heating at around 250 ° C., and in the case of double-sided coating, the film interface disappears, and the adhesion between the films is achieved. However, at this stage, the low-melting point inorganic component having high temperature stability hardly causes the reaction. Next, at the time of heating at 750 ° C., the low-melting-point inorganic component is softened and melts depending on the low-melting-point inorganic component species, and the low-melting-point inorganic components that are in contact with each other are bonded. As a result, the opposing coatings are integrated to complete the bonding between the steel plates. Therefore, it is important that the low-melting point inorganic component softens or melts in the heating stage near 750 ° C.

  In the low melting point inorganic component having a high softening point temperature as in Condition No. 9 in Table 1, even if the low melting point inorganic components are in contact with each other, the softening does not proceed in the temperature range of 750 ° C. A sufficient contact area cannot be obtained between the components. Therefore, the bonds between the low melting point inorganic components are not sufficiently formed. As a result, the adhesive strength cannot be obtained.

  On the other hand, in the low melting point inorganic component having a low softening point temperature as in condition number 1 to condition number 8 in Table 1, if the low melting point inorganic components are in contact with each other, the softening proceeds in the temperature range of 750 ° C. A constant contact area can be obtained between the low melting point inorganic components. Therefore, a bond between the low melting point inorganic components is formed. As a result, adhesive strength can be obtained.

  The reason why a certain 750 ° C adhesive strength can be obtained even for low melting point inorganic components with a softening point temperature higher than 750 ° C, which is a heating temperature such as 880 ° C and 1000 ° C, has not been fully elucidated, but softening Even with low melting point inorganic components with a spot temperature of 880 ° C or 1000 ° C, some kind of softening-like reaction occurs in the temperature range of 750 ° C, and the low melting point inorganic components bind to each other, so film integration and steel plate adhesion are not realized. I guess.

The reason why the adhesive strength at 250 ° C is 10 kg / cm ² or more is that the adhesive strength that can be handled without peeling is specified in the manufacturing process after temporary fixing by low-temperature bonding and until final fixing. . The adhesive strength of 1 kg / cm ² or higher at 750 ° C. is defined as the adhesive strength that does not peel off after being incorporated in an electrical device.

As the low melting point inorganic component of the present invention, a low melting point glass frit, water glass or a mixture of these colloidal silicas can be used.
When the low-melting-point inorganic component to be used is an inorganic powder, the particle size is also important. If the particle size is too large, coarse protrusions are formed on the surface of the film, and contact between the films is hindered. In order to achieve sufficient contact between the coatings or between the powders, the average particle size of the low-melting-point inorganic component used is desirably 20 μm or less. In particular, the average particle size is desirably 4 μm or less, and more desirably 3 μm or less.

Next, the present inventors examined the mixing ratio of the low melting point inorganic component and the resin.
First, a number of non-oriented electrical steel sheets having a plate thickness of 0.35 mm and an insulating coating mainly composed of magnesium chromate on the surface were prepared. On the other hand, as a low melting point inorganic component, a low melting point glass frit (B ₂ O ₃ = 30%, SiO ₂ = 20%, BaO = 30%, Na _{2 with} an average particle diameter of 3 μm and a softening point temperature of 550 ° C. O = 10%, ZnO = 10%) and a water emulsion liquid with a resin composition of epoxy resin: acrylic resin: phenolic resin = 20: 5: 3 (mass%) and a solid fraction of 20 mass%. It applied using the coater. At this time, it prepared so that the mixing ratio of resin with respect to a glass frit might become various values. The coating amount was adjusted to 5 g / m ² per side and dried at a plate temperature of 150 ° C. A test piece was cut out from the sample thus prepared. Subsequently, 250 degreeC adhesive strength and 750 degreeC adhesive strength were measured. The results are shown in Table 2.

From Table 2, from Condition No. 2 to Condition No. 6, that is, when the resin / glass frit mixing ratio is 20% or more and 500% or less, the 250 ° C. adhesive strength is 10 kg / cm ² or more and the 750 ° C. adhesive strength is It can be seen that both values are good at 1 kg / cm ² . On the other hand, when the resin / glass frit mixing ratio of Condition No. 1 is 10%, the 250 ° C. adhesive strength is 5 kg / cm ² and the 750 ° C. adhesive strength is 0.5 kg / cm ² , which are both low. Further, in the condition No. 7 where the resin / glass frit mixing ratio was 700%, the 250 ° C. adhesive strength was as good as 40 kg / cm ² , but the 750 ° C. adhesion was as low as 0.5 kg / cm ² .
From the above, it was found that both the 250 ° C. adhesive strength and the 750 ° C. adhesive strength were good when the resin / glass frit mixing ratio was 20% to 500%.

  Moreover, the present inventors consider the following mechanism about the reason why the adhesive strength depends on the resin ratio to the low-melting-point inorganic component. The resin shares the adhesive function when heated at 250 ° C., and the low melting point inorganic component shares the adhesive function when heated at 750 ° C. Therefore, by considering whether or not the two are in a state where they can function at each heating temperature, a mechanism of the resin / low-melting-point inorganic component ratio dependence on the adhesive strength can be estimated. That is, the surface occupancy state of the organic resin that performs the adhesive function when heated at 250 ° C. and the low melting point inorganic component that performs the adhesive function when heated at 750 ° C. may be considered.

When the ratio of the resin to the low melting point inorganic component is small, for example, in the case of condition number 1 in Table 2, the low melting point inorganic component occupies most of the surface, and the resin is almost peeped on the surface. Absent. In such a state, even if the coatings are overlaid and pressurized, even if heated at 250 ° C., a sufficient contact area cannot be obtained between the resins, so that the resin that should achieve adhesion between the coatings cannot function sufficiently. . Therefore, the adhesive strength at 250 ° C. is a small value (in the case of condition number 1, 250 ° C. adhesive strength = 5 kg / cm ² ). Even if the low-melting point inorganic component is softened and melted in the state where sufficient adhesion is not realized when heated at 250 ° C and the low-melting inorganic component is softened and melted, contact between the coatings is not realized sufficiently when heated at 250 ° C in advance. However, contact and bonding between low melting point inorganic components cannot be realized sufficiently. As a result, the 750 ° C. adhesive strength also becomes a small value (in the case of condition number 1, 750 ° C. adhesive strength = 0.5 kg / cm ² ). By such a mechanism, when the ratio of the resin is too small with respect to the low melting point inorganic component, both the 250 ° C. adhesive strength and the 750 ° C. adhesive strength show low values.

On the other hand, when the mixing ratio of the resin to the low-melting-point inorganic component is large, the resin is sufficiently present on the surface of the coating, and the resin performs a sufficient adhesive function when heated at 250 ° C., so that a large adhesive strength can be obtained (conditions In the case of 7, 250 ° C. adhesive strength = 40 kg / cm ² ). However, when heating at 750 ° C., the low melting point inorganic component that should exhibit an adhesive function is not sufficiently present on the surface of the coating, so the 750 ° C. adhesive strength is small (in the case of condition number 7, 750 ° C. adhesive strength = 0.5 kg / cm ² ).
In addition, by setting the coefficient of linear thermal expansion of the low-melting-point inorganic component from 30 ° C to 300 ° C to 10 × 10 ^-7 (° C ^-1 ) or more and 150 × 10 ^-7 (° C ^-1 ) or less, it is Variations in characteristics can also be prevented.

The inventors prepared a coated steel sheet and an iron core made of the steel sheet under the following conditions, and investigated the magnetic properties. First, a large number of non-oriented electrical steel sheets having a plate thickness of 0.5 mm and having no insulating coating on the surface were prepared. On the other hand, as a low melting point inorganic component, a low melting point glass frit having an average particle diameter of 5 μm and various thermal expansion coefficients, and a resin composition of epoxy resin: acrylic resin: phenol resin = 10: 4: 5 (mass%) ) And a water emulsion solution having a solid fraction of 20% by mass were mixed and applied using a roll coater. The mixing ratio of the resin to the glass frit was set to 200% as a solid content ratio. The coating amount was 10 g / m ² per side, and the film was dried at a plate temperature of 150 ° C.

A ring-shaped sample with an inner diameter of 10.16 cm (4 inches) and an outer diameter of 12.7 cm (5 inches) was prepared from these samples, and 20 sheets were stacked and heated at a pressure of 10 kg / cm ² and a temperature of 250 ° C for 4 hours. Thus, a film-bonded iron core was produced. Next, the iron core was annealed at a temperature of 750 ° C. for 2 hours without being pressurized. Finally, the iron loss value was measured at a frequency of 50 Hz and a magnetic flux density of 1.5 Tesla. The results are shown in Table 3.

From Table 3 to Condition No. 2 to Condition No. 9, the coefficient of linear thermal expansion of the low melting point inorganic component from 30 ° C to 300 ° C is 10 × 10 ^-7 (° C ^-1 ) or more and 150 × 10 ^-7 (° C ^-1 ) or less. It can be seen that the iron loss in forming the iron core after annealing is smaller than 3.1 (W / kg) and good. On the other hand, when a glass frit with a linear thermal expansion coefficient of condition number 1 of 160 x 10 ^-7 (° C ^-1 ) is used, the iron loss value is large at 3.27 (W / kg). Even when a glass frit with an expansion coefficient of 5 × 10 ⁻⁷ (° C. ⁻¹ ) was used, the iron loss value was 3.26 (W / kg). From the above, when the linear thermal expansion coefficient of the low melting point inorganic component from 30 ° C to 300 ° C is 10 × 10 ^-7 (° C ^-1 ) or more and 150 × 10 ^-7 (° C ^-1 ) or less, It was found that the iron loss during iron core molding was good.

  The present inventors consider the following mechanism as to why the iron loss in the iron core after annealing depends on the linear thermal expansion coefficient of the low melting point inorganic component. Pressurization and heating adhesion at 250 ° C. softens and melts the resin in the film, and in the case of double-sided coating, the film interface disappears and adhesion between the films is realized. However, at this stage, the low-melting point inorganic component having high temperature stability hardly causes the reaction. Next, at the time of heating at 750 ° C., the low-melting-point inorganic component is softened and melts depending on the low-melting-point inorganic component species, and the low-melting-point inorganic components that are in contact with each other are bonded. As a result, the opposing coatings are integrated to complete the bonding between the steel plates. Then, after cooling to room temperature, the iron loss value is measured. What should be considered here is the problem of stress generated in the formed iron core when the steel sheet surface is fully bonded at a high temperature of 750 ° C. and cooled to room temperature.

In general, when a stress acts on an iron core, the magnetic properties deteriorate. Here, first, the relationship between the thermal expansion coefficient of the substance and the stress will be described. In general, when a substance with a large coefficient of thermal expansion and a substance with a small coefficient of thermal expansion are bonded at a high temperature and cooled to room temperature, a substance with a large coefficient of thermal expansion has a tensile stress, and a substance with a small coefficient of thermal expansion has a compressive stress. Each work. The linear thermal expansion coefficient of electrical steel sheets is approximately 100 × 10 ⁻⁷ (° C. ⁻¹ ) for both directional and non-oriented electrical steel sheets. On the other hand, the coefficient of thermal expansion of the low melting point inorganic component used in the experiment is 5 × 10 ⁻⁷ (° C. ⁻¹ ) to 160 × 10 ⁻⁷ (° C. ⁻¹ ). Therefore, tensile stress acts on the formed iron core when using inorganic powder with a smaller thermal expansion coefficient than steel plate, and compressive stress when using inorganic powder with larger thermal expansion coefficient than steel plate. It will be.

  Considering this experiment, in the case of inorganic powder having the largest linear thermal expansion coefficient under condition number 1, a large compressive force is exerted on the formed iron core, and the smallest linear thermal expansion coefficient is obtained under condition number 10. In the case of the inorganic powder, it is presumed that a large tensile stress acts on the formed iron core. Because of the difference in the coefficient of linear thermal expansion between the steel sheet and the largest thermal stress, the molded cores of Condition No. 1 and Condition No. 10, which are presumed to have the largest stress, have an iron loss value due to this stress application. It is thought that it was big. On the other hand, in the case of condition number 2 to condition number 9, the thermal expansion coefficient of the inorganic powder used was different from that of the steel sheet, but the difference was small, so the tensile stress and compressive stress on the formed iron core worked Even if it is, the value is small, and as a result, it can be estimated that there is no significant effect on the iron loss value.

The low-melting-point inorganic component of the present invention contributes to adhesion development after strain relief annealing, and is preferably a low-melting glass having a softening point of 750 ° C. or lower, which is a normal strain relief annealing temperature. The low melting point glass can be softened and melted during strain relief annealing, solidified by cooling, and the two plates can be bonded after strain relief annealing. The composition of the low melting point glass is SiO ₂ -B ₂ O ₃ -R ₂ O (R is alkali metal), P ₂ O ₅ -R ₂ O (R is alkali metal), SiO ₂ -PbO-B ₂ Examples thereof include O ₃ series, B ₂ O ₃ —Bi ₂ O ₃ series, SiO ₂ —B ₂ O ₃ —ZnO series, SnO—P ₂ O ₅ series, SiO ₂ —B ₂ O ₃ —ZrO ₂ series. In particular, the SiO ₂ —B ₂ O ₃ —R ₂ O (R is alkali metal) system is preferable because it is lead-free and has high adhesive strength after strain relief annealing.

  The low melting point inorganic component may be added as a liquid like water glass. The water glass is particularly preferably sodium silicate. As an advantage of using water glass, since the powder particles are not included, there is no unevenness due to the particles on the coated surface, and a smooth surface can be easily obtained. In particular, when sodium silicate is used, a high strength of 1.0 MPa or more can be obtained as the adhesive strength after strain relief annealing. Further, when potassium silicate is used, a high strength of about 4.0 to 7.0 MPa is obtained as the adhesive strength before strain relief annealing.

  As the low-melting-point inorganic component of the present invention, a material obtained by further mixing colloidal silica with the above-described inorganic component can also be used. By mixing colloidal silica or the like, the viscosity when the inorganic component is softened during strain relief annealing can be adjusted. Further, even when colloidal silica remains unsoftened during strain relief annealing, it functions as an aggregate in the film, and can increase the adhesive strength after strain relief annealing.

  The resin that can be applied to the present invention is not limited to a thermosetting resin that causes a curing reaction when steel plates are bonded to each other by pressure and heating, such as a phenol resin or an epoxy resin, an acrylic resin or a methacrylic resin. A thermoplastic resin that does not cause a curing reaction even when heated can be applied. Either thermoplastic or thermosetting resin can be applied, but it is desirable to have an adhesive action.

The resin of the present invention is softened at room temperature to 300 ° C., but in consideration of blocking properties, etc., preferably 50 ° C. or more, 80 ° C. or more, 100 ° C. or more, in particular, heating at 120 ° C. or more and 300 ° C. or less, It is preferable to soften to such an extent that fluidity is exhibited. The softening to such an extent that the fluidity is expressed is based on a viscosity of 1 × 10 ⁸ dPa · s or less. As a mechanism that the resin cured by baking on the steel sheet surface is softened by heating at 300 ° C. or less, the cured resin is a thermoplastic resin, and the temperature at which the thermoplastic develops is 120 ° C. or more and 300 ° C. or less. There are some cases.

  Further, as a softening mechanism when the resin is thermosetting, there is a case where the resin is softened to a rubber state or a fluid state by heating to a temperature higher than the glass transition temperature. In particular, in the case of a resin cured by baking at a low temperature of 200 ° C or less for a short time of several tens of seconds or less, the resin undergoes a glass transition while softening once through a crosslinking reaction that forms a three-dimensional skeleton by heating. However, when heated to a higher temperature, the crosslinking reaction may proceed again to be cured.

  The acrylic modified epoxy resin emulsion previously blended with the latent curing agent used as the resin of the present invention is a compound in which the latent curing agent is blended with the epoxy resin, and then the acrylic resin is chemically reacted to form the epoxy resin and the latent curing agent. The mixture was coated to make an emulsion. The epoxy resin here refers to a resin having two or more epoxy groups in the monomer, and is bisphenol A type, bisphenol F type, bisphenol AD type, naphthalene type, phenol novolak type, orthocresol novolak type, glycidyl ester type. And alicyclic type. Examples of the latent curing agent include dicyandiamide, melamine, organic acid dihydrazide, amine imide, keramine, tertiary amine salt, imidazole salt, boron trifluoride amine salt, microcapsule type curing agent, molecular sieve type curing agent and the like. The acrylic resin is transformed into a mixed system of the epoxy resin and the epoxy resin curing agent.

  The term “modification” as used herein refers to chemically bonding an acrylic resin to the surface of the epoxy resin and epoxy resin curing agent mixture. As the acrylic resin used for such modification, one or more of methacrylic acid, methacrylic acid ester, acrylic acid, acrylic acid ester, styrene, vinyl acetate and the like are polymerized or copolymerized. The mixing ratio of the epoxy resin and the latent epoxy resin curing agent varies greatly depending on the type of epoxy resin and the type of curing agent, but usually 0.05 to 2 parts by mass is appropriate for 1 part by mass of the epoxy resin. It is essential that the mixed liquid mainly composed of an acrylic-modified epoxy resin emulsion with a latent curing agent in advance be baked in an incomplete state after being applied to the steel sheet surface. There is no generation, and after being sheared and laminated, it is in a state of being bonded by pressure and heating. Usually, it can be baked in an incomplete state by drying at a furnace temperature of 100 to 300 ° C. for 10 to 90 seconds.

Furthermore, a siloxane polymer can be used as a resin that is softened by heating. A siloxane polymer is a polymer whose main skeleton is composed of inorganic bonds of Si—O—Si. Si, like C, like Si-CH ₃ , Si-C ₆ H ₅ , and Si-H, Si can be directly chemically bonded to organic groups and H. A modified siloxane polymer can be obtained.

Of the four bonds of Si, one of which forms a Si-R bond (R is an organic group or H) and the remaining three are Si-O bonds is called a T nucleus. Among the T nuclei, those having 3 bonded to Si via O, that is, Rsi (-O-Si) ₃ are called T3 nuclei. Si nuclides can be examined by NMR. In general, Si nuclei forming a siloxane polymer include D nuclei and Q nuclei in addition to T nuclei. In the D nucleus, two of Si's four bonds form Si-R (R is an organic group or H) bond, and the remaining two are Si-O bonds. The Q nucleus is a Si-O bond in four of the four Si bonds.

When Si in the T3 drawing repeats bonding according to a certain rule, a ladder molecule as shown in FIG. 2 is formed.
A polymer composed of ladder-like molecules is entangled with ladder-like molecular chains by coating and baking, and a hardened surface state without stickiness or blocking is obtained. Molecular chains that have been entangled at 100 ° C or higher will break and become fluid. As long as fluidity is exhibited, Si nuclei bonded with epoxy groups may be included in addition to Si nuclei bonded with methyl groups.

  The siloxane polymer of the present invention is obtained by hydrolysis in the presence of one or both of organotrialkoxysilane and organotrichlorosilane under a hydrochloric acid catalyst. Organotrialkoxysilanes include triethoxysilane, trimethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, isobutyltrimethoxysilane, Isobutyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, methacryloxypropyltrimethoxysilane, methacryloxypropyltriethoxysilane, glycidoxypropyltrimethoxysilane, glycidoxypropyltriethoxysilane, aminopropyltrimethoxysilane And aminopropyltriethoxysilane. Examples of the organotrichlorosilane include methyltrichlorosilane, ethyltrichlorosilane, and phenyltrichlorosilane.

  One or both of organotrialkoxysilane and organotrichlorosilane may be hydrolyzed after being dispersed in an organic solvent. As the solvent, various alcohols such as methanol, ethanol, propanol and butanol, acetone, toluene, xylene and the like can be used. The mass ratio of the organic solvent to the organoalkoxysilane at the time of hydrolysis is desirably 1: 0.5 to 1: 2.

  Hydrolysis is performed by adding 0.1 to 1 times as much water as the number of moles of all alkoxy groups in the starting material. Hydrochloric acid is added as a hydrolysis catalyst. When organotrichlorosilane is used as a raw material, hydrochloric acid is produced as a by-product by adding water, and hydrolysis is carried out under a hydrochloric acid catalyst without any special treatment. There are also good things.

  The hydrolyzed sol is usually converted into a siloxane polymer by promoting the polycondensation reaction by a process such as concentration. Concentration is performed by removing the organic solvent and by-product alcohol with a rotary evaporator, etc., so that the mass of the concentrate is about 15 to 60% of the mass of the solution before concentration. From the viewpoint of As a method other than concentration, an alkali such as KOH may be added and refluxed under a nitrogen atmosphere or the like to promote the polycondensation reaction, thereby obtaining a siloxane polymer. The obtained siloxane polymer is diluted about 1.5 to 10 times with an organic solvent or water to obtain a coating solution. Usually, the state which adhere | attaches by pressurization heating is obtained by baking at 100 to 200 degreeC for 15 to 120 second.

  The resin and the low-melting-point inorganic component in the present invention do not show at least apparent melting in the film of the present invention depending on conditions such as heating and annealing atmosphere, and the grains remain as they are. Although it may appear, there is no problem in the present invention as long as the bonding function is exhibited by the heating and annealing.

  The present invention can be applied to any type of magnetic steel sheet produced by ordinary rolling / annealing, such as a directional magnetic steel sheet and a non-oriented magnetic steel sheet, but is particularly applicable to a non-oriented electrical steel sheet for motor cores. In that case, the effect can be exhibited most.

  In a normal manufacturing method for grain-oriented electrical steel sheets and non-oriented electrical steel sheets, a surface coating is formed on the steel sheet surface by finish annealing for both steel sheets. In the case of a grain-oriented electrical steel sheet, a phosphate-based film containing a silica component is formed, and in the case of a non-oriented electrical steel, a chromate-based film is formed. In particular, in the case of grain-oriented electrical steel sheets, a manufacturing method that forms a film mainly composed of forsterite silicate during finish annealing, a manufacturing method that does not intentionally form the film, and a forsterite film that has been formed is pickled. There is a manufacturing method that removes by means. The present invention can be applied with or without these various surface coatings.

The electrical steel sheet with a heat-resistant adhesive insulating coating of the present invention is applied to the electrical steel sheet with a coating solution containing the heat-resistant adhesive insulating coating composition by a method such as a roll coater, bar coater, flow coater, dip coater or spray. The coating amount is preferably 1 g / m ² or more and 30 g / m ² or less, particularly preferably 2 g / m ² or more and 10 g / m ² or less.

  The heat-resistant adhesive insulating coating composition is preferably a mixture of a resin and a low-melting-point inorganic component, but may be a mixture in which both are dispersed in a lump form, or a mixture in which both layers are separated and applied. Low-melting-point inorganic components may be dispersed in the form of dots or stripes in the organic matrix, or the organic components are dispersed in dots or stripes in the inorganic matrix due to siloxane bonds. May be.

  The film thickness is desirably 0.5 μm or more and 20 μm or less per side. If the film thickness is less than 0.5 μm, it is difficult to sufficiently cover the entire surface of the steel sheet, so that sufficient adhesive strength cannot be obtained. On the other hand, if the film thickness is more than 20 μm, the space factor greatly decreases when pressed and heated. Therefore, the film thickness is preferably 0.5 μm or more and 20 μm or less.

  The coating composition of the present invention is first baked and cured after application to the surface of the magnetic steel sheet so that stickiness and blocking do not occur. After application, an electrical steel sheet with a heat-resistant adhesive insulating coating can be produced by baking at 50 to 200 ° C. This step may be performed immediately before punching out the iron core or laminating the iron core, but it is particularly preferable to apply the magnetic steel sheet in a so-called pre-coated state at the time of manufacturing the steel sheet in terms of simplifying the core manufacturing process. When the steel sheet pieces punched out from the steel sheet into a desired shape are laminated and blocked, the resin is softened by heating to a temperature higher than the baking temperature.

  When the magnetic steel sheet pieces having the coating of the present invention on both sides are laminated and hot pressing is performed, the resin softened by heating at the time of the hot pressing is integrated, so that the electromagnetic steel sheet pieces can be bonded during cooling. Become.

  In addition, when magnetic steel sheet pieces having the coating of the present invention only on one side are laminated in the same direction, the resin component softened by heating spreads uniformly on the surface of the electromagnetic steel sheet pieces without the coating layer of the present invention. Sometimes it can be glued. Since a high temperature hot press is expensive, the hot press temperature is desirably 300 ° C. or lower. The pressure of the hot press is preferably 0.1 MPa or more and 50 MPa or less, and particularly preferably 1 MPa or more and 20 MPa or less. When the pressure of the hot press is low, sufficient adhesiveness cannot be obtained, so that it is difficult to integrate as an iron core. When the pressure of hot pressing is high, the adhesive layer may flow and protrude from the interlayer.

  The electromagnetic steel sheet of the present invention can be integrated as an iron core by punching into a desired shape and then laminating, pressing and heating. Thereafter, even when strain relief annealing is performed as necessary, the adhesion between the laminated steel sheets is maintained. The temperature for strain relief annealing is usually 650 ° C. or higher and 850 ° C. or lower, and often 700 ° C. or higher and 800 ° C. or lower.

In addition, since the coating film of this invention has adhesiveness even if annealing, such as strain relief annealing, is not performed, it can be utilized also for the iron core which does not perform strain relief annealing. That is, it can be used as an adhesive coating for both strain relief annealing and non-strain relief annealing.
In the case of strain relief annealing, it is also possible to use caulking or fixing with a jig together when fixing by pressurization or heating.

Acrylic resin: Epoxy resin: Phenolic resin = 10: 4: 3 (mass%) Composition with glass frit with various particle sizes at a softening point temperature of 450 ° C in a resin water dispersion with a solid content ratio of 20 mass% A prepared liquid was prepared. The resin / glass frit mixing ratio in the liquid containing glass frit was set to 200%. This coating solution was applied to a non-oriented electrical non-oriented electrical steel sheet having a plate thickness of 0.5 mm and no insulating coating on the steel sheet surface using a roll coater so that the coating amount was 6 g / m ² per side. Subsequently, it dried at the drying temperature of 150 degreeC, and cooled. The film thickness per side was 10 μm. A test piece having a length of 10 cm in the rolling direction and a length of 3 cm in the direction perpendicular to the rolling direction was cut out from the sample thus prepared. Then, heated to 250 ° C. at 1cm long in the short side portions, pressurized with overlapping area 3 cm ² overlapped two specimens at 10 kg / cm ² state, held for 60 seconds, cooled, 250 ° C. adhesion strength A test specimen for measurement was prepared. Further, a part of the test piece for measuring the adhesive strength at 250 ° C. was heated to 750 ° C. under no load, kept for 2 hours, and cooled to prepare a test piece for measuring the adhesive strength at 750 ° C. The test piece thus prepared was measured for adhesive strength using a tensile tester. The results are shown in Table 4.

From Table 4, in the sample group in which the average particle diameter of the glass frit of Condition No. 1 to Condition No. 5 is 2 μm to 20 μm, the 250 ° C. adhesive strength is 10 kg / cm ² or more and the 750 ° C. adhesive strength is also 1 kg / cm. for ^two or more and in the range of good, for samples average particle size of the glass frit 25μm of conditions No. 6, becomes a smaller value as 250 ° C. adhesion strength can not be measured 750 ° C. the adhesive strength at 5 kg / cm ^2, better It wasn't.
The example in which the average particle size of the glass frit is 20 μm or less is superior to the comparative example in which the average particle size is 25 μm.

Acrylic resin: Epoxy resin: Phenolic resin = 11: 3: 4 (mass%) Composition in a resin water dispersion with a solid content ratio of 20 mass%, composition is B ₂ O ₃ = 25 mass%, SiO ₂ = 65 mass% , Na ₂ O = 10% by mass, and a mixture of glass frit (Example) having a coefficient of linear thermal expansion of 40 × 10 ⁻⁷ (° C. ⁻¹ ) at 30 ° C. to 300 ° C. The composition is B ₂ O ₃ = 50 mass%, SiO ₂ = 25 mass%, K ₂ O = 25 mass%, and the linear thermal expansion coefficient from 30 ° C. to 300 ° C. is 170 × 10 ⁻⁷ (° C. ⁻¹ ). A liquid in which glass frit (comparative example) was mixed was prepared. Glass frit having an average particle diameter of 10 μm was used. In addition, the resin / glass frit mixing ratio in the liquid containing glass frit was set to 100%.

Using a roll coater, the coating amount is 8 g / m ² per side for a finish annealed non-oriented electrical steel sheet with a thickness of 0.5 mm and a magnesium chromate-based insulation coating on the steel sheet surface. It was applied as follows. Subsequently, it dried at the drying temperature of 140 degreeC, and cooled. The film thickness per side was 6 μm. A ring-shaped sample with an inner diameter of 10.16 cm (4 inches) and an outer diameter of 12.7 cm (5 inches) was prepared from the sample thus prepared, and 20 sheets were stacked, with a pressure of 10 kg / cm ² and a temperature of 250 ° C. for 4 hours. It heated and produced the film adhesion type iron core. Next, the iron core was annealed at a temperature of 750 ° C. for 2 hours without being pressurized. Finally, the iron loss value was measured at a frequency of 50 Hz and a magnetic flux density of 1.5 Tesla. The results are shown in Table 5.

From Table 5, the iron loss of the iron core made using glass frit with a linear thermal expansion coefficient of condition number 1 of 40 × 10 ^-7 (° C ^-1 ) is good at 3.05 (W / kg) The iron loss of an iron core produced using a glass frit with a linear thermal expansion coefficient of 170 × 10 ⁻⁷ (° C. ⁻¹ ) in Condition No. 2 was a large value of 3.27 (W / kg), which was not good. Thus, it can be seen that the example according to the present invention is superior to the comparative example.

The following four types of coating solutions were prepared.
Coating liquid A
40 parts by mass of an acrylic modified epoxy resin emulsion containing 20% by mass of a latent curing agent and 5 parts by mass of methyl ethyl ketone were blended with 100 parts by mass of water. The glass transition temperature of the resin obtained by applying and baking this coating solution was 104 ° C. and softened at 120 ° C. or higher.

Coating solution B
100 parts by weight of water, 40 parts by weight of an acrylic resin emulsion, 40 parts by weight of an epoxy resin emulsion, and 4 parts by weight of an amine epoxy curing agent were blended. The resin obtained by applying and baking this coating solution was softened at 150 ° C. or higher.

Coating liquid C
Hydrolysis was performed by adding dropwise an aqueous solution prepared by mixing 35.3 g of water and 1.04 g of 35% hydrochloric acid into a liquid for mixing 178 g of methyltriethoxysilane and 138 g of ethanol. The hydrolyzed liquid was concentrated using a rotary evaporator until the solvent disappeared at 58 ° C. The mass of the concentrate was 30% of the solution mass before concentration. The mass average molecular weight of this concentrate was 10,000. Since this concentrate showed a yarn property, it is considered that methyltriethoxysilane is polymerized in the form of a chain polymer. When this concentrate was heat-treated at 70 ° C. for 15 minutes, it solidified, but softened from around 180 ° C. 200 parts by mass of ethanol was blended with 100 parts by mass of the concentrate.

Coating liquid D
178 g of methyltriethoxysilane and 152 g of tetramethoxysilane are dispersed in 270.3 g of 2-ethoxyethanol. A coating solution was prepared by using 4.8 g of acetic acid as a catalyst and hydrolyzing by adding 36 g of water. This siloxane polymer was not softened by heating.

In Table 6, the temperature described in parentheses after the glass composition in the middle stage of the coating solution is the glass softening temperature. All the glasses described in Table 6 are powders having an average particle diameter of 2 μm. In Examples and Comparative Examples, each coating solution was applied to both surfaces of a non-oriented electrical steel sheet having a thickness of 0.5 mm with a roll coater and baked in a furnace set at 70 ° C. for 15 minutes. The coating amount was 7 g / m ² . In any case, there was no stickiness of the film surface after baking.

Using two test pieces having a width of 3 cm and a length of 10 cm, a part of the test piece was overlapped so that the area of the bonded portion was 6 cm ² and hot pressing was performed. Prior to hot pressing, the film applied to areas other than the bonded area was scraped off. Two test pieces were bonded by a hot press at 200 ° C. for 1 minute and 10 MPa. The strain relief annealing was performed in nitrogen at 750 ° C. for 2 hours. The adhesive strength before and after strain relief annealing was evaluated using the shear tensile strength, which is the horizontal strength of the bonded surface.

  In Comparative Example 1, since the glass had a softening temperature higher than the stress relief annealing temperature, there was no adhesion after annealing. Since Comparative Example 2 was a type in which the resin was not softened by heating, it could not be bonded by hot pressing. Since Comparative Example 3 did not contain low-melting glass, adhesion after strain relief annealing could not be obtained.

The following four types of coating solutions were prepared.
Coating liquid A
40 parts by mass of an acrylic modified epoxy resin emulsion containing 20% by mass of a latent curing agent and 5 parts by mass of methyl ethyl ketone were blended with 100 parts by mass of water. The glass transition temperature of the resin obtained by applying and baking this coating solution was 104 ° C. and softened at 120 ° C. or higher.

Coating liquid B
100 parts by weight of water, 40 parts by weight of an acrylic resin emulsion, 40 parts by weight of an epoxy resin emulsion, and 4 parts by weight of an amine epoxy curing agent were blended. The resin obtained by applying and baking this coating solution was softened at 150 ° C. or higher.

Coating liquid C
Hydrolysis was performed by adding dropwise an aqueous solution prepared by mixing 35.3 g of water and 1.04 g of 35% hydrochloric acid into a liquid for mixing 178 g of methyltriethoxysilane and 138 g of ethanol. The hydrolyzed solution was concentrated using a rotary evaporator at 58 ° C. until no solvent was produced. The mass of the concentrate was 30% of the solution mass before concentration. The mass average molecular weight of this concentrate was 10,000. Since this concentrate showed a yarn property, it is considered that methyltriethoxysilane is polymerized in the form of a chain polymer. When this concentrate was heat-treated at 70 ° C. for 15 minutes, it solidified, but softened from around 180 ° C. 200 parts by mass of ethanol was blended with 100 parts by mass of the concentrate.

In Examples, the coating solutions A to C were diluted with water, and various water glasses were added to prepare coating solutions. In Examples and Comparative Examples, each coating solution was applied on both sides of a 0.5 mm-thick non-oriented electrical steel sheet with a roll coater and baked in a furnace set at 70 ° C. for 15 minutes. The coating amount was 10 g / m ² . In any case, there was no stickiness of the film surface after baking.

Using two test pieces each having a width of 3 cm and a length of 10 cm, a part of the test piece was overlapped and subjected to hot pressing so that the area of the bonded portion was 6 cm ² . Prior to hot pressing, the applied film other than the bonded part was scraped off. Two test pieces were bonded by hot pressing at 200 ° C. for 1 minute and 10 MPa. The strain relief annealing was performed in nitrogen at 750 ° C. for 2 hours. The adhesive strength before and after strain relief annealing was evaluated using the shear tensile strength, which is the horizontal strength of the bonded surface.

The coating liquid D described in Example 3 was produced. 10 parts by mass of polyester spherical particles having an average particle diameter of 4 μm and a softening temperature of 200 ° C. were mixed and dispersed with respect to 100 parts by mass of the coating solution D. After applying to a non-oriented electrical steel sheet having a surface coating with an inorganic-organic mixed treatment solution with a roll coater, it was baked for 2 minutes in a furnace set at 100 ° C. The coating amount was 10 g / m ² . Using two test pieces each having a width of 3 cm and a length of 10 cm, a part of the test piece was overlapped and subjected to hot pressing so that the area of the bonded portion was 6 cm ² . Prior to hot pressing, the applied film other than the bonded part was scraped off. Two test pieces were bonded by a hot press at 230 ° C. for 1 minute and 10 MPa. The strain relief annealing was performed in nitrogen at 750 ° C. for 2 hours. The adhesive strength before and after strain relief annealing was evaluated using the shear tensile strength, which is the horizontal strength of the bonded surface. The adhesive strength before and after strain relief annealing was 1.0 MPa and 2.1 MPa, respectively.

  According to the present invention, after punching or shearing, it can be bonded by pressurization and heating to be integrated as an iron core, and the adhesive ability can be maintained even after further strain relief annealing. A steel plate can be provided. Iron core can be integrated without welding and caulking, and iron loss deterioration due to welding and caulking can be avoided. Adhesion and insulation are maintained even after strain relief annealing, so the iron core has excellent magnetic properties. Can be produced.

In the present invention, electrical steel sheets can be laminated and then bonded by pressurization and heating (in the present invention, it refers to a heat treatment at room temperature or higher and 300 ° C. or lower unless otherwise specified), and thereafter annealing treatment such as strain relief annealing ( in the present invention, in particular it refers to a heat treatment at 300 ° C. greater unless otherwise specified.) be subjected to those about the heat adhesive coating compositions which can maintain adhesion ability.

Things present invention, the heat resistance of the adhesive insulating coating of adhesive insulating film having an electromagnetic steel sheet is improved, even if the stress relief燒鈍provide heat adhesive insulating the film adhesion state and the insulating properties are maintained It is.

In order to solve the above problems, the present invention uses the following means.
(1) A heat resistant adhesive insulating coating comprising a resin having a softening point temperature of room temperature to 300 ° C. and a low melting point inorganic component having a softening point temperature of 1000 ° C. or less ,
The mixing ratio of the resin to the low melting point inorganic component is 100% or more and 500% or less by mass fraction,
The low-melting-point inorganic component is a low-melting-point glass frit, water glass, or a mixture of them with colloidal silica, and the average particle size of the low-melting-point inorganic component is 20 μm or less at 30 ° C. to 300 ° C. The coefficient of linear thermal expansion is not less than 10 × 10 ^-7 (° C ^-1 ) and not more than 150 × 10 ^-7 (° C ^-1 ),
Furthermore, 250 ° C. adhesive strength = 10 kg / cm ² or more and 750 ° C. adhesive strength = 1 kg / cm ² or more .

( 2 ) The heat-resistant adhesive insulating coating according to ( 1 ), wherein the low-melting-point inorganic component is SiO ₂ —B ₂ O ₃ —R ₂ O-based low-melting glass (R is an alkali metal).
( 3 ) The heat-resistant adhesive insulating coating according to ( 1 ), wherein the water glass is sodium silicate.
(4) the resin is an epoxy resin, an acrylic resin, a phenol resin, previously latent acrylic curing agent was formulated modified epoxy resin emulsion was baked in incomplete mixing solution mainly composed resins or siloxane polymer, They comprise one or more selected from and wherein (1), wherein the heat-adhesive insulating film.

Claims (14)

  A heat resistant adhesive insulating coating comprising a resin having a softening point temperature of room temperature to 300 ° C and a low melting point inorganic component having a softening point temperature of 1000 ° C or less. ^2. The heat-resistant adhesive insulating coating according to claim 1, wherein 250 ° C. adhesive strength = 10 kg / cm ² or more and 750 ° C. adhesive strength = 1 kg / cm ² or more. 2. The heat-resistant adhesive insulation according to claim 1, wherein the coefficient of linear thermal expansion at 30 to 300 ° C. is 10 × 10 ⁻⁷ (° C. ⁻¹ ) or more and 150 × 10 ⁻⁷ (° C. ⁻¹ ) or less. Coating.   2. The heat resistant adhesive insulating coating according to claim 1, wherein the low melting point inorganic component is a low melting point glass frit, water glass, or a mixture of them with colloidal silica.   The heat-resistant adhesive insulating coating according to claim 4, wherein the low-melting-point inorganic component has an average particle size of 20 µm or less.   The heat-resistant adhesive insulating coating according to claim 4, wherein the mixing ratio of the resin to the low-melting-point inorganic component is 20% to 500% by mass fraction. The heat-resistant adhesive insulating coating according to claim 4, wherein the low-melting-point inorganic component is SiO ₂ -B ₂ O ₃ -R ₂ O-based low-melting glass (R is an alkali metal).   The heat-resistant adhesive insulating coating according to claim 4, wherein the water glass is sodium silicate.   The resin is selected from an epoxy resin, an acrylic resin, a phenol resin, a resin in which a mixed liquid mainly composed of an acrylic modified epoxy resin emulsion previously blended with a latent curing agent is baked in an incomplete state, or a siloxane polymer 1 The heat resistant adhesive insulating coating according to claim 1, comprising seeds or two or more kinds.   A magnetic steel sheet with a heat-resistant adhesive insulating coating, comprising the coating according to claim 1 on at least one side of the steel plate.   11. The electrical steel sheet with a heat-resistant adhesive insulating coating according to claim 10, wherein the thickness of the heat-resistant adhesive insulating coating is from 0.5 μm to 20 μm.   An iron core using the electrical steel sheet with a heat-resistant adhesive insulating coating according to claim 10.   An electromagnetic steel sheet with a heat-resistant adhesive insulating coating, wherein the electromagnetic steel sheet according to claim 10 is laminated and pressure-fixed to produce an electromagnetic steel sheet laminate, and then annealed at 600 to 900 ° C. to obtain an integrated iron core. A method of manufacturing an iron core using a steel plate.   The iron core using the electrical steel sheet with a heat-resistant adhesive insulating coating according to claim 13, wherein at least in the pressure fixing stage, heating is performed for adhesive fixing, fixing is performed by caulking or a jig, or a combination thereof is used. Manufacturing method.

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